CN109843853B

CN109843853B - Composition and method for manufacturing device using the same

Info

Publication number: CN109843853B
Application number: CN201780063876.2A
Authority: CN
Inventors: 菅优介; 榎本智至
Original assignee: Toyo Gosei Co Ltd
Current assignee: Toyo Gosei Co Ltd
Priority date: 2016-10-17
Filing date: 2017-10-13
Publication date: 2022-09-20
Anticipated expiration: 2037-10-13
Also published as: WO2018074382A1; US11142495B2; TWI725241B; TW201821402A; KR102278416B1; US20200048191A1; JPWO2018074382A1; KR20190059327A; CN109843853A; JP6847121B2

Abstract

The invention provides an onium salt and a composition which are suitable for a resist composition for a lithography process using 1 st active energy line such as electron beam or extreme ultraviolet ray and 2 nd active energy line such as UV, have high sensitivity and excellent pattern characteristics such as LWR. The present invention provides an onium salt represented by any one of the following general formula (1), the following general formula (2), the following general formula (11), and the following general formula (12). [ CHEM 1 ]

Description

Composition and method for manufacturing device using the same

Technical Field

One embodiment of the present invention relates to a composition. In another embodiment of the present invention, a method for manufacturing a device using the composition.

Background

In recent years, photolithography using a photoresist has been actively used to form semiconductor elements and manufacture of display devices such as Liquid Crystal Displays (LCDs) and organic EL displays (OLEDs). For the packaging of the electronic parts and electronic products, light having a wavelength of 365nm as active energy rays, i-rays (405nm) and g-rays (436nm) having longer wavelengths, and the like are widely used.

With the high integration of equipment, demands for refinement of lithography technology have been increasing, and light having a very short wavelength, such as KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), extreme ultraviolet (EUV, wavelength 13.5nm), and Electron Beam (EB), tends to be used for exposure. Since the photolithography technique using light having such a short wavelength, particularly EUV or electron beam, can realize single patterning, a resist composition exhibiting high sensitivity to EUV or electron beam is increasingly required in the future.

As the exposure source is shortened, there is a growing demand for resist compositions having improved lithographic characteristics such as sensitivity to the exposure source and resolution with which patterns of minute dimensions can be reproduced. As a resist composition satisfying such a requirement, a chemically amplified resist is known (patent document 1).

However, conventional chemically amplified resist compositions have low EUV or electron beam absorption, and it is difficult to satisfy characteristics of sensitivity, resolution, and pattern performance at the same time. In particular, it is difficult to overcome the low productivity due to low sensitivity caused by small absorption, and the resist pattern destruction and the deterioration of Line Width Roughness (LWR) of the line pattern which are generated with the miniaturization of the resist resolution line width.

In order to solve the above problems, in order to improve productivity of EUV or electron beam lithography, a photosensitized chemically amplified resist composition for use in producing an acid and a sensitizer by lithography using a 1 st active energy ray such as EUV or electron beam, and then irradiating a 2 nd active energy ray such as visible light or ultraviolet light has been proposed. (patent documents 2 to 3 and non-patent document 1)

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 9-90637

Patent document 2: japanese patent No. 5881093

Patent document 3: japanese patent laid-open publication No. 2015-172741

Non-patent document

Non-patent document 1: OfSPIE Vol.9776977607

Disclosure of Invention

Problems to be solved by the invention

However, in the case where the resist reaction is promoted by the above-mentioned 2 nd active energy line using the photosensitized chemically amplified resist composition utilizing the above-mentioned photosensitization reaction, since a photoinduced electron transfer reaction is generated between the sensitizer (electron donor) and the photoacid generator (electron acceptor), there is a possibility that an acid is generated even by an electron transfer reaction of several nm in some cases. This may prevent the acid diffusion control agent from reacting with the resist composition and causing unintended diffusion of the acid even when the acid diffusion control agent is contained in the resist composition. This may cause pattern degradation such as LWR degradation. On the other hand, when a large amount of an acid diffusion controller is added to suppress pattern deterioration, there are problems as follows: the amount of the photosensitizer produced in the process of producing the photosensitizing agent by the action of the acid produced by the above-mentioned 1 st active energy ray is small, and therefore, the sensitization reaction hardly occurs even if the irradiation is made to 1J/cm, for example ² With such a large amount of energy, the effect of promoting the resist reaction is small.

In view of the above circumstances, an object of several embodiments of the present invention is to provide a photoacid generator and a composition which are excellent in pattern characteristics such as sensitivity and LWR. More specifically, the object is to provide an onium salt which is most suitable as a photoacid generator to be used for irradiation with a particle beam, an electromagnetic wave or the like. Further, it is an object of the present invention to provide a composition containing the onium salt and a specific resin whose solubility in a developer is changed by an action of an acid. Further, it is an object of the present invention to provide an onium salt which is most suitable as a photoacid generator used when a 1 st active energy ray such as a particle beam or an electromagnetic wave is irradiated and then exposed to a 2 nd active energy ray such as ultraviolet light or visible light. Further, it is an object to provide a composition containing the onium salt and a specific resin whose solubility in a developer is changed by the action of an acid. Further, it is an object of some embodiments of the present invention to provide a photoacid generator containing the onium salt, and a composition containing the photoacid generator. Further, it is an object to provide a method for producing a device using the composition.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that an onium salt having a specific structure does not significantly absorb the 2 nd active energy ray such as ultraviolet rays or visible light, and that the onium salt is converted into a ketone derivative which absorbs the 2 nd active energy ray by a structural change caused by an acid generated by the 1 st active energy ray such as a particle beam or an electromagnetic wave, thereby completing several embodiments of the present invention.

By using a photoacid generator containing the onium salt as a resist composition, it was found that the 2 nd active energy ray can generate an acid with higher efficiency, and thus is superior in high sensitivity and pattern characteristics such as LWR, compared with the resist composition described in patent document 3, which utilizes a photosensitization reaction occurring between an electron donor and an electron acceptor.

One embodiment of the present invention to solve the above problems is an onium salt represented by any one of the following general formula (1), the following general formula (2), the following general formula (11), and the following general formula (12).

[ CHEM 1 ]

In the above formula (1), R ¹¹ And R ¹² Each independently is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent; a linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms which may have a substituent; an aryl group having 6 to 14 carbon atoms which may have a substituent; and a heteroaryl group having 4 to 12 carbon atoms which may have a substituent; any of the above.

R is as defined above ¹¹ 、R ¹² Any two or more of the aryl groups bonded to the sulfonium group may form a ring structure directly with a single bond or may form a ring structure via one selected from an oxygen atom, a sulfur atom, a nitrogen atom-containing group and a methylene group, and the ring structure may include R and R ¹¹ 、R ¹² Sulfur atom (S) bonded to aryl group bonded to sulfonium group ⁺ )，

R is as defined above ¹¹ And R ¹² At least 1 methylene group in (a) may be substituted with a divalent heteroatom-containing group.

R ¹³ And R ¹⁴ Each independently is any one selected from the group consisting of an alkyl group, a hydroxyl group, a mercapto group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an arylthio group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a (meth) acryloyloxy group, a hydroxyl (poly) alkyleneoxy group, an amino group, a cyano group, a nitro group and a halogen atom, and the number of carbon atoms when having a carbon atom is 1 to 12, and they may have a substituent.

R ¹⁵ And R ¹⁶ Each independently is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent; a linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms which may have a substituent; an aryl group having 6 to 14 carbon atoms which may have a substituent; and a heteroaryl group having 4 to 12 carbon atoms which may have a substituent; any of the above.

R is as defined above ¹⁵ And R ¹⁶ The ring structures may be formed by direct bonding to each other by a single bond, or may be formed by bonding to each other via any one selected from an oxygen atom, a sulfur atom, and an alkylene group.

R is as defined above ¹⁵ And R ¹⁶ At least 1 methylene group in (a) may be substituted with a divalent heteroatom-containing group.

The quaternary carbon atom having 2Y's directly bonded thereto and the 2 aryl groups directly bonded to the quaternary carbon atom form a 5-membered ring structure in which the 2 aryl groups directly bonded to the quaternary carbon atom are directly bonded to each other, or form a 6-membered ring structure by bonding through 1 atom. L is ³ Is selected from straightA bond, a methylene group, a sulfur atom, a nitrogen atom-containing group, and an oxygen atom are selected from any one of the above.

L ² Is selected from a direct bond; a branched or cyclic alkylene group having 1 to 12 carbon atoms; an alkenylene group having 1 to 12 carbon atoms; an arylene group having 6 to 14 carbon atoms; a heteroarylene group having 4 to 12 carbon atoms; and a group in which these groups are bonded via an oxygen atom, a sulfur atom or a nitrogen atom-containing group; any of the above.

Y is an oxygen atom or a sulfur atom.

h and i are each independently an integer of 1 to 3.

J is an integer of 0 to 4 when h is 1, j is an integer of 0 to 6 when h is 2, and j is an integer of 0 to 8 when h is 3.

K is an integer of 0 to 5 when i is 1, k is an integer of 0 to 7 when i is 2, and k is an integer of 0 to 9 when i is 3.

X ^- Represents a monovalent counter anion.

In the above formula (2), R ¹³ ～R ¹⁶ 、L ² 、L ³ Y, h-k and X ^- Each independently selected from R of the above formula (1) ¹³ ～R ¹⁶ 、L ² 、L ³ Y, h-k and X ^- Each of the same options.

R ¹⁷ Is selected from aryl groups which may have a substituent; and a heteroaryl group which may have a substituent, R ¹⁷ The aryl groups bonded to the iodonium groups may be bonded to each other to form a ring structure together with the iodine atoms to which they are bonded.

In the above formula (11), R ¹¹ ～R ¹⁶ 、L ² Y, h-k and X ^- Each independently selected from R of the above formula (1) ¹¹ ～R ¹⁶ 、L ² Y, h-k and X ^- Each of the same options.

L ⁴ And L ⁵ Each independently is any one selected from a direct bond, an alkenylene group having 2 carbon atoms, and an alkynylene group having 2 carbon atoms.

In the above formula (12), R ¹³ ～R ¹⁷ 、L ² Y, h-k and X ^- Each independently of the otherIs selected from the group consisting of R of the above formula (2) ¹³ ～R ¹⁷ 、L ² Y, h-k and X ^- Each of the same options.

Another embodiment of the present invention is a sulfonium salt represented by the following general formula (6). The following description shows monocationic groups, but polycationic groups may be used.

[ CHEM 2 ]

In the above formula (6), R ¹¹ ～R ¹⁶ 、X ^- And Y are each independently selected from R of the above formula (1) ¹¹ ～R ¹⁶ 、X ^- And Y are the same options.

R ¹⁸ Is any one selected from the group consisting of an alkyl group, a hydroxyl group, a mercapto group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an arylthio group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, (meth) acryloyloxy group, a hydroxyl (poly) alkyleneoxy group, an amino group, a cyano group, a nitro group and a halogen atom, the number of carbon atoms when having carbon is preferably 1 to 12, and they may have a substituent.

e is an integer of 0 to 4, f is an integer of 0 to 4, and g is an integer of 0 to 5.

In another embodiment of the present invention, the photoacid generator (a) contains at least an onium salt represented by any one of the general formula (1), the general formula (2), the general formula (11), and the general formula (12). The photoacid generator (a) generates an acid by exposure.

One embodiment of the present invention to solve the above problems is a composition containing the photoacid generator (a) and an acid-reactive compound.

Preferably, the composition further comprises an acid diffusion controller.

The acid-reactive compound is preferably a resin (B) whose solubility in the developer is changed by the action of an acid,

the resin (B) is a composition having at least one of the units represented by the following (3a) to (3 d). The onium salt contained in the photoacid generator (a) is a monocationium as described above, but may be a polycation.

[ CHEM 3]

In the above formulae (3a) to (3d), R ¹ Is any one selected from a hydrogen atom, an alkyl group and a halogenated alkyl group.

R ² And R ³ Each independently is a linear, branched or cyclic alkyl group.

R ⁴ Is a linear, branched or cyclic alkyl group which may have a substituent.

R is as defined above ² 、R ³ And R ⁴ At least 2 of them may form a ring structure directly with a single bond or through any one selected from methylene groups.

R ⁵ And R ⁶ Each independently represents a hydrogen atom, and a linear, branched or cyclic alkyl group is selected from any of the above groups.

R ⁷ Is a linear, branched or cyclic alkyl group which may have a substituent.

R is as defined above ⁵ 、R ⁶ And R ⁷ At least 2 of them may form a ring structure directly with a single bond or through any one selected from methylene groups.

L ¹ Is any one selected from a direct bond, a carbonyloxy group, a carbonylamino group, a linear, branched or cyclic alkylenecarbonyloxy group which may have a substituent, and an alkylenecarbonylamino group.

R ⁸ Each independently selected from alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylthio, alkylAny one of sulfinyl, alkylsulfonyl, amino, cyano, nitro, and halogen atoms.

l is an integer of 1 to 2.

M is an integer of 0 to 4 when l is 1, and m is an integer of 0 to 6 when l is 2.

N is an integer of 1 to 5 when l is 1, or 1 to 7 when l is 2.

M + n is 1 to 5 when l is 1, and m + n is 1 to 7 when l is 2.

Another aspect of the present invention is a method for manufacturing a device, including: a step of forming a resist film by applying the composition to a substrate; irradiating the resist film with a 1 st active energy ray; irradiating the resist film irradiated with the 1 st active energy ray with a 2 nd active energy ray; and a step of obtaining a pattern by developing the resist film irradiated with the 2 nd active energy ray.

Effects of the invention

According to several aspects of the present invention, there can be provided a composition using a resist composition used for a lithography process using a 1 st active energy line such as a particle beam or an electromagnetic wave and a 2 nd active energy line such as ultraviolet light or visible light, and containing an onium salt having high sensitivity and excellent pattern characteristics such as LWR as an acid generator. In addition, a beam of particles or electromagnetic waves may be provided. Particularly, a resist composition having high sensitivity to the 1 st active energy ray such as electron beam or extreme ultraviolet ray, and a method for manufacturing a device using the same.

Detailed Description

The present invention will be specifically described below, but the present invention is not limited thereto.

<1> onium salt and photoacid generator

The onium salt according to one embodiment of the present invention is represented by any one of the general formula (1), the general formula (2), the general formula (11), and the general formula (12). The photoacid generator (hereinafter, also referred to as "photoacid generator (a)") contains at least 1 kind of the onium salt. The onium salt is a sulfonium salt or an iodonium salt.

The onium salt according to one embodiment of the present invention has a specific structure such as acetal or thioacetal, and thus does not have significant absorption of the above-mentioned 2 nd active energy ray such as ultraviolet ray or visible light. On the other hand, the acetal or thioacetal of the onium salt is deprotected by an acid generated by the 1 st active energy ray such as a particle beam or an electromagnetic wave and converted to a ketone derivative without impairing the function as a photoacid generator. The ketone derivative has an absorption function for the 1 st active energy ray and the 2 nd active energy ray. Since the ketone derivative is generated in the exposed portion of the resist film to which the 1 st active energy ray is irradiated, the amount of acid generated in the exposed portion by the 1 st active energy ray can be increased by further irradiating the 2 nd active energy ray.

In the above formula (1), R ¹¹ And R ¹² Each independently is preferably selected from linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms which may have a substituent; a linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms which may have a substituent; an aryl group having 6 to 14 carbon atoms which may have a substituent; and a heteroaryl group having 4 to 12 carbon atoms which may have a substituent; any of the above.

As R ¹¹ And R ¹² Specific examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms in (1) include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantan-1-yl group, an adamantan-2-yl group, a norbornane-1-yl group and a norbornane-2-yl group.

R ¹¹ And R ¹² The alkyl group of (A) may contain in the skeleton thereof a group selected from the group consisting of-O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH-, -N (R) -, -N (Ar) -, -S-, -SO-and-SO ₂ 1 divalent heteroatom containing group in-in place of at least 1 methylene group. Wherein the sulfur atom (S) of the sulfonium group ⁺ ) Preferably, the divalent hydrocarbon group is bonded to the hydrocarbon group without being directly bonded to the heteroatom-containing group. R and Ar will be explained below.

R ¹¹ And R ¹² Examples of the alkenyl group in (1) include those in which at least 1 carbon-carbon single bond of the alkyl group is substituted by a carbon-carbon double bond.

As R ¹¹ And R ¹² The aryl group having 6 to 14 carbon atoms which may have a substituent(s) includes, specifically, a monocyclic aromatic hydrocarbon group; and a fused polycyclic aromatic hydrocarbon group obtained by at least bicyclic condensation of the monocyclic aromatic hydrocarbon. These aryl groups may have a substituent.

Examples of the monocyclic aromatic hydrocarbon group include groups having a skeleton such as benzene.

Examples of the fused polycyclic aromatic hydrocarbon group include groups having a skeleton such as indene, naphthalene, azulene, anthracene, phenanthrene, and the like.

As R ¹¹ And R ¹² Examples of the heteroaryl group having 4 to 12 carbon atoms which may have a substituent(s) include a group having a skeleton containing at least one member selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom in place of at least 1 carbon atom of the aryl group.

Examples of the heteroaryl group include a monocyclic aromatic heterocyclic group; and a fused polycyclic aromatic heterocyclic group obtained by condensing at least one of the monocyclic aromatic heterocyclic groups with the aromatic hydrocarbon group, the aliphatic heterocyclic group, or the like. These aromatic heterocyclic groups may have a substituent.

Examples of the monocyclic aromatic heterocyclic group include groups having a skeleton such as furan, pyrrole, imidazole, pyran, pyridine, pyrimidine, and pyrazine.

Examples of the fused polycyclic aromatic heterocyclic group include groups having a skeleton such as indole, purine, quinoline, isoquinoline, benzopyran, phenoxazine, xanthene, acridine, phenazine, and carbazole.

As R ¹¹ And R ¹² Examples of the substituent which may be present (hereinafter, also referred to as "substituent 1") include a hydroxyl group, a cyano group, a mercapto group, a carboxyl group, a carbonyl group, an alkoxy group (-OR), an acyl group (-COR), an alkoxycarbonyl group (-COOR), an aryl group (-Ar), an aryloxy group (-OAr), an amino group (-NH-), an alkylamino group (-NHR), a dialkylamino group (-N (R)) ₂ ) Arylamino (-NHAr), diarylamino (-N (Ar) ₂ ) N-alkyl-N-arylamino (-NRAr) phosphino group, silyl group, halogen atom, trialkylsilyl group (-Si- (R) ₃ ) And a silyl group in which at least 1 alkyl group of the trialkylsilyl group is substituted with ArAlkylthio (-SR), arylthio (-SAr), and the like, but is not limited thereto. R and Ar will be explained below.

The 1 st substituent may be a group having a polymerizable group such as a (meth) acryloyl group.

R is as defined above ¹¹ 、R ¹² Any two or more of the aryl groups bonded to the sulfonium group may form a ring structure directly with a single bond or may form a ring structure via one selected from an oxygen atom, a sulfur atom, a nitrogen atom-containing group and a methylene group, and the ring structure may include R and R ¹¹ 、R ¹² Sulfur atom (S) of sulfonium group bonded to aryl group bonded to sulfonium group ⁺ ). Wherein the sulfur atom (S) of the sulfonium group ⁺ ) Preferably to the above divalent hydrocarbon group without being directly bonded to a heteroatom-containing group.

Examples of the "nitrogen atom-containing group" include nitrogen atom-containing 2-valent groups such as aminodiyl (-NH-), alkylaminodiyl (-NR-), arylaminodiyl (-NAr-). R and Ar will be explained below.

In the formula (1), the aryl group bonded to the sulfonium group is a portion indicated by an arrow below.

[ CHEM 4 ]

The above R in the 1 st substituent and the like is preferably an alkyl group having 1 or more carbon atoms. Further, the number of carbon atoms is more preferably 20 or less. Specific examples of the alkyl group having 1 or more carbon atoms include, for example, a linear alkyl group such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-octyl group, and a n-decyl group; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl and 2-ethylhexyl groups; alicyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantan-1-yl, adamantan-2-yl, norbornane-1-yl and norbornane-2-yl; a silyl-substituted alkyl group in which one hydrogen of the above groups is substituted with a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, or a dimethylethylsilyl group; an alkyl group in which at least 1 hydrogen atom of these groups is substituted with a cyano group, a fluoro group, or the like; and the like.

Ar in the above-mentioned substituent 1 and the like is preferably an aryl group or a heteroaryl group. Heteroaryl is an aryl group containing 1 or more heteroatoms in the ring structure. Specific examples of Ar include groups having 20 or less carbon atoms such as phenyl, biphenyl, triphenyl, quaterphenyl, naphthyl, anthracenyl, phenanthryl, pentalenyl, indenyl, indacenyl (indacenyl), acenaphthenyl (acenaphtyl), fluorenyl, heptenylyl, tetracenyl, pyrenyl, curolyl, tetraphenyl, furyl, thienyl, pyranyl, sulfonylpyranyl, pyrrolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridyl, isobenzofuryl, benzofuryl, isochromenyl, chromenyl, indolyl, isoindolyl, benzimidazolyl, xanthenyl, acridinyl (aquadinyl), and carbazolyl.

R ¹¹ And R ¹² When the onium salt is a low molecular weight compound having the substituent (1) as described above, R ¹¹ And R ¹² The number of carbon atoms (C) of (C) is preferably 1 to 20 inclusive of the number of carbon atoms of the 1 st substituent.

The onium salt in one embodiment of the present invention may be a polymer component bonded to a part of the polymer as a unit of the resin, that is, a unit containing an onium salt structure, or may be a polymer component contained as a unit of the polymer. In the case of a polymer component, the 1 st substituent may be the main chain of the polymer. R ¹¹ And R ¹² When the 1 st substituent is a main chain of the polymer, R ¹¹ And R ¹² The number of carbon atoms of (b) is the number of carbon atoms other than the number of carbon atoms of the polymer main chain. When the onium salt in one embodiment of the present invention is a polymer component, the weight average molecular weight of the entire polymer component is preferably adjusted to 2000 to 200000.

In the present invention, the low-molecular compound is a compound having a weight average molecular weight of less than 2000, and the polymer component is a component having a weight average molecular weight of 2000 or more.

As R ¹¹ And R ¹² From increasingFrom the viewpoint of stability, aryl groups are preferred.

R ¹³ And R ¹⁴ Each independently is any one selected from the group consisting of an alkyl group, a hydroxyl group, a mercapto group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an arylthio group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a (meth) acryloyloxy group, a hydroxyl (poly) alkyleneoxy group, an amino group, a cyano group, a nitro group and a halogen atom, and when having carbon, the number of carbon atoms is preferably 1 to 12, and they may have a substituent (hereinafter, also referred to as "substituent 2").

As R ¹³ And R ¹⁴ The alkyl group in (1) may be a linear, branched or cyclic alkyl group, and specifically, the same alkyl group as that of the alkyl group of R as the substituent (1) is exemplified. As R ¹³ And R ¹⁴ As the aryl and heteroaryl in (1), there may be mentioned ¹¹ And R ¹² The same group as that for the aryl group and heteroaryl group of Ar in the substituent 1. R ¹³ And R ¹⁴ Examples of the alkoxy group in (1) include the same groups as those mentioned for the alkoxy group (-OR) in the substituent (1).

As R ¹³ And R ¹⁴ Examples of the hydroxy (poly) alkyleneoxy group in (1) include polyoxyethylene group and polypropylene group.

As R ¹³ And R ¹⁴ Examples of the halogen atom in (2) include a fluorine atom, a chlorine atom, an iodine atom and the like.

R ¹³ And R ¹⁴ In the alkyl group (C), the skeleton may contain the above-mentioned R ¹¹ And R ¹² The same group as the heteroatom-containing group in (1) replaces at least 1 methylene group. Among them, continuous bonding of hetero atoms such as-O-, -S-and-O-S-is not preferred.

As R ¹³ And R ¹⁴ Examples of the substituent (2) which may be present include the same substituents as those mentioned for the substituent (1).

R ¹³ And R ¹⁴ When the onium salt is a low molecular weight compound having the substituent (2) as described above, R ¹³ And R ¹⁴ The number of carbon atoms of (2) is preferablyThe number of carbon atoms including the 2 nd substituent is 1 to 12. R ¹³ And R ¹⁴ When the 2 nd substituent of (2) is a polymer main chain, R ¹³ And R ¹⁴ The number of carbon atoms of (b) is the number of carbon atoms other than the main chain of the polymer.

As R ¹⁴ Preferably, an alkyl group is mentioned. In addition, with respect to and having Y and R ¹⁴ When the quaternary carbon atom to which the arylene group of (2) is bonded is ortho-or para-position, preferred examples thereof include electron-donating groups such as aryl, alkoxy, alkylthio, aryloxy, arylthio, amino, and alkylamino. These groups are preferred because they increase the absorbance at 365 nm.

As R ¹⁵ And R ¹⁶ Preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent; a linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms which may have a substituent; an aryl group having 6 to 14 carbon atoms which may have a substituent; and optionally substituted heteroaryl having 4 to 12 carbon atoms selected from the group consisting of R ¹¹ And R ¹² Respectively the same option.

As R ¹⁵ And R ¹⁶ Examples of the substituent (hereinafter, also referred to as "substituent 3") include the same substituents as those mentioned for the substituent 1.

From the viewpoint of synthesis, the above R is preferred ¹⁵ And R ¹⁶ The same is true.

A quaternary carbon atom having 2Y's directly bonded thereto and 2 aryl groups (Ar represented by an arrow in the following formula) ^a And Ar ^b ) A 5-membered ring structure formed by directly bonding 2 aryl groups directly bonded to the quaternary carbon atom; or a 6-membered ring structure bonded via 1 atom. L is ³ Selected from the group consisting of a direct bond, a methylene group, a sulfur atom, a nitrogen atom-containing group, and an oxygen atom. L is ³ Examples of the nitrogen atom-containing group in (2) include the same nitrogen atom-containing groups as those mentioned aboveA group.

[ CHEM 5 ]

Here, the onium salt has a structure represented by the following formula when a 5-membered ring structure in which aryl groups are directly bonded to each other is formed.

[ CHEM 6 ]

In addition, when a 6-membered ring structure in which aryl groups are bonded to each other through 1 atom is formed, the onium salt may be represented by the following formula.

[ CHEM 7 ]

L ² Preferably selected from linear, branched or cyclic alkylene groups having 1 to 12 carbon atoms; an alkenylene group having 1 to 12 carbon atoms; an arylene group having 6 to 12 carbon atoms; a heteroarylene group having 4 to 12 carbon atoms; and a group in which these groups are bonded via an oxygen atom, a sulfur atom or a nitrogen atom-containing group; any of the above. L is ² The alkylene, alkenylene, arylene and heteroarylene of (1) may be exemplified by the above-mentioned R ¹¹ The alkyl, alkenyl, aryl and heteroaryl of (a) are groups having a valence of 2. L is ² The nitrogen atom-containing group of (2) may be mentioned with R ¹¹ The nitrogen atom-containing group of (1) is the same group.

In the general formula (1), k and j are each preferably 0 to 3 independently of one another, and more preferably 0 to 2 independently of one another, from the viewpoint of ease of synthesis.

In the above general formula (2), R ¹³ ～R ¹⁶ 、X ^- 、Y、L ² 、L ³ H to k are each independently selected from R of the formula (1) ¹³ ～R ¹⁶ 、X ^- 、Y、L ² 、L ³ And h to k are the same as each other.

R ¹⁷ Preferably an aryl group having 6 to 12 carbon atoms which may have a substituent; a heteroaryl group having 4 to 12 carbon atoms which may have a substituent. R ¹⁷ The aryl groups bonded to the iodonium groups may be bonded to each other to form a ring structure together with the iodine atoms to which they are bonded. R ¹⁷ Is selected from the group consisting of ¹¹ And aryl and heteroaryl of (a) are each the same option. R ¹⁷ The substituent (1) includes the same substituents as those mentioned above.

In the above general formula (2), the aryl group to which the above iodonium group is bonded is a moiety represented by the following arrow.

[ CHEM 8 ]

A 5-membered ring structure formed by direct bonding of 2 quaternary carbon atoms to which Y is directly bonded and 2 aryl groups directly bonded to the quaternary carbon atoms, and direct bonding of 2 aryl groups directly bonded to the quaternary carbon atoms; or via L ³ A 6-membered ring structure formed by bonding.

In the above general formula (11), R ¹¹ ～R ¹⁶ 、L ² Y, h-k and X ^- Each independently selected from R of the above formula (1) ¹¹ ～R ¹⁶ 、L ² Y, h-k and X ^- Each of the same options.

L ⁴ And L ⁵ Each independently is any one selected from a direct bond, an alkenylene group having 2 carbon atoms, an alkynylene group having 2 carbon atoms, and a carbonyl group. That is, the quaternary carbon atom to which 2Y are directly bonded and 2 aryl groups may be directly bonded, or may be bonded via an alkenylene group having 2 carbon atoms or an alkynylene group having 2 carbon atoms, but the quaternary carbon atom and the aryl group have a structure in which at least 1 bond via an alkenylene group having 2 carbon atoms or an alkynylene group having 2 carbon atoms is contained.

In the formula (11), the aryl group bonded to the sulfonium group is a portion indicated by an arrow below.

[ CHEM 9 ]

In the aforementioned general formula (12), R ¹³ ～R ¹⁷ 、L ² Y, h-k and X ^- Each independently selected from R of the above formula (2) ¹³ ～R ¹⁷ 、L ² Y, h-k and X ^- Each of the same options.

L ⁴ And L ⁵ Each independently is any one selected from a direct bond, an alkenylene group having 2 carbon atoms, an alkynylene group having 2 carbon atoms, and a carbonyl group. That is, the quaternary carbon atom to which 2Y are directly bonded and 2 aryl groups may be directly bonded, or may be bonded via an alkenylene group having 2 carbon atoms or an alkynylene group having 2 carbon atoms, and the unit may have a structure in which at least 1 bond via an alkenylene group having 2 carbon atoms or an alkynylene group having 2 carbon atoms is present.

In the above formula (12), the aryl group to which the above iodonium group is bonded is a moiety represented by the following arrow.

[ CHEM 10 ]

In the above formula (1), (2), (11), or (12), Y is an oxygen atom or a sulfur atom.

h and i are each independently an integer of 1 to 3.

J is an integer of 0 to 4 when h is 1, j is an integer of 0 to 6 when h is 2, and j is an integer of 0 to 8 when h is 3; k is an integer of 0 to 5 when i is 1, k is an integer of 0 to 7 when i is 2, and k is an integer of 0 to 9 when i is 3.

In the formula (1) or (2), when i and/or h is 2, the onium salt has a naphthalene ring. In the naphthalene ring, Y may be bonded to any of the 1-to 8-positions of the quaternary carbon to be bonded.

For example, in the formula (1), (2), (11), or (12), when i and/or h is 3, the onium salt has at least one of an anthracene ring, a phenanthrene ring, and a naphtalene ring. In this case, in the phenanthrene ring and the naphthonaphthalene ring, Y may be bonded to any position of 1 to 10 positions of the quaternary carbon to be bonded.

In some embodiments of the present invention, the onium salt is exemplified by onium salts having a sulfonium cation and an iodonium cation shown below. However, the present invention is not limited to these embodiments.

[ CHEM 11 ]

[ CHEM 12 ]

[ CHEM 13 ]

[ CHEM 14 ]

[ CHEM 15 ]

One embodiment of the present invention is preferably a sulfonium salt represented by the following formula (6).

[ CHEM 16 ]

In the above formula (6), R ¹¹ ～R ¹⁶ 、X ^- And Y are each independently selected from R of the above formula (1) ¹¹ ～R ¹⁶ 、X ^- And Y are each phaseThe same option.

X ^- Is an anion. The anion is not particularly limited, and examples thereof include anions such as sulfonate anion, carboxylate anion, imide anion, methide anion, carbon anion, borate anion, halogen anion, phosphate anion, antimonate anion, and arsenate anion.

More specifically, as the anion, ZA is preferably mentioned ^a- 、(Rf) _b PF _(6-b) ^- 、R ¹⁹ _c BA _(4-c) ^- 、R ¹⁹ _c GaA _(4-c) ^- 、R ²⁰ SO ₃ ^- 、(R ²⁰ SO ₂ ) ₃ C ^- Or (R) ²⁰ SO ₂ ) ₂ N ^- Are typical anions. Has more than 2 Rf and R ¹⁹ And R ²⁰ In case, 2 of Rf, R ¹⁹ 2 of (1) and R ²⁰ 2 of which may be bonded to each other to form a ring, respectively.

Z represents a phosphorus atom, a boron atom or an antimony atom. A represents a halogen atom (preferably a fluorine atom).

P represents an atom, F represents a fluorine atom, B represents a boron atom, and Ga represents a gallium atom.

S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom.

Rf is preferably an alkyl group in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms, and the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group substituted with fluorine to be Rf include a straight-chain alkyl group (such as methyl, ethyl, propyl, butyl, pentyl, and octyl), a branched-chain alkyl group (such as isopropyl, isobutyl, sec-butyl, and tert-butyl), and a cycloalkyl group (such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl). In Rf, the ratio of substitution of hydrogen atoms of these alkyl groups by fluorine atoms is preferably 80 mol% or more, more preferably 90% or more, and particularly preferably 100% based on the number of moles of hydrogen atoms of the original alkyl group.

Particularly preferred Rf includes CF ₃ ^- 、CF ₃ CF ₂ ^- 、(CF ₃ ) ₂ CF ^- 、CF ₃ CF ₂ CF ₂ ^- 、CF ₃ CF ₂ CF ₂ CF ₂ ^- 、(CF ₃ ) ₂ CFCF ₂ ^- 、CF ₃ CF ₂ (CF ₃ )CF ^- And (CF) ₃ ) ₃ C ^- . b Rf's are independent of each other and may be the same or different.

R ¹⁹ Represents a phenyl group having a hydrogen atom part of which is substituted with at least 1 halogen atom or electron withdrawing group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the electron-withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group. Among them, a phenyl group in which 1 hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable. C number of R ¹⁹ Are independent of each other and thus may be the same or different from each other.

R ²⁰ The alkyl group may be a linear, branched or cyclic alkyl group, and the aryl group may have no substituent or a substituent.

a represents an integer of 4 to 6. b represents an integer of 1 to 5, preferably 2 to 4, and particularly preferably 2 or 3. c represents an integer of 1 to 4, preferably 4.

As a result of ZA _a ^- Examples of the anion represented by the formula (I) include SbF ₆ ^- 、PF ₆ ^- And BF ₄ ^- The anions shown, and the like.

As a compound of (Rf) _b PF _(6-b) ^- Examples of the anion represented by the formula (CF) ₃ CF ₂ ) ₂ PF ₄ ^- 、(CF ₃ CF ₂ ) ₃ PF ₃ ^- 、((CF ₃ ) ₂ CF) ₂ PF ₄ ^- 、((CF ₃ ) ₂ CF) ₃ PF ₃ ^- 、(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ^- 、(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- 、((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^- 、((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- 、(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ^- And (CF) ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ^- The anions shown, and the like. Among them, preferred is a Compound of (CF) ₃ CF ₂ ) ₃ PF ₃ ^- 、(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- 、((CF ₃ ) ₂ CF) ₃ PF ₃ ^- 、((CF ₃ ) ₂ CF) ₂ PF ₄ ^- 、((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- And ((CF) ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^- The anion shown.

As a group consisting of R ¹⁹ _c BA _(4-c) ^- Examples of the anion represented by (C) ₆ F ₅ ) ₄ B ^- 、((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^- 、(CF ₃ C ₆ H ₄ ) ₄ B ^- 、(C ₆ F ₅ ) ₂ BF ₂ ^- 、C ₆ F ₅ BF ₃ ^- And (C) ₆ H ₃ F ₂ ) ₄ B ^- The anions shown, and the like. Among them, preferred is a compound represented by (C) ₆ F ₅ ) ₄ B ^- And ((CF) ₃ ) ₂ C ₆ H ₃ ) ₄ B ^- The anion shown.

As a group consisting of R ¹⁹ _c GaA _(4-c) ^- Examples of the anion represented by (C) ₆ F ₅ ) ₄ Ga ^- 、((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^- 、(CF ₃ C ₆ H ₄ ) ₄ Ga ^- 、(C ₆ F ₅ ) ₂ GaF ₂ ^- 、C ₆ F ₅ GaF ₃ ^- And (C) ₆ H ₃ F ₂ ) ₄ Ga ^- The anions shown, and the like. Among them, preferred is a compound represented by (C) ₆ F ₅ ) ₄ Ga ^- And ((CF) ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^- The anion shown.

As a group consisting of R ²⁰ SO ₃ ^- Examples of the anion represented by the formula (I) include trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, nonafluorobutanesulfonate anion, pentafluorophenylsulfonate anion, p-toluenesulfonate anion, benzenesulfonate anion, camphorsulfonate anion, methanesulfonate anion, ethanesulfonate anion, propanesulfonate anion and butanesulfonate anion. Among them, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, benzenesulfonate anion and p-toluenesulfonate anion are preferable.

As a group of (R) ²⁰ SO ₂ ) ₃ C ^- Examples of the anion represented by the formula (CF) ₃ SO ₂ ) ₃ C ^- 、(C ₂ F ₅ SO ₂ ) ₃ C ^- 、(C ₃ F ₇ SO ₂ ) ₃ C ^- And (C) ₄ F ₉ SO ₂ ) ₃ C ^- The anions shown, and the like.

As a group of (R) ²⁰ SO ₂ ) ₂ N ^- Examples of the anion represented by the formula (CF) ₃ SO ₂ ) ₂ N ^- 、(C ₂ F ₅ SO ₂ ) ₂ N ^- 、(C ₃ F ₇ SO ₂ ) ₂ N ^- And (C) ₄ F ₉ SO ₂ ) ₂ N ^- The anion shown, and the like. In addition, as a compound represented by (R) ²⁰ SO ₂ ) ₂ N ^- The anion represented by (A) is not particularly limited but may be 2 (R) ²⁰ SO ₂ ) The corresponding moieties are bonded to each other to form a cyclic imide of a ring structure.

As the monovalent anion, besides the above anions, perhalogenated acid ion (ClO) can be used ₄ ^- 、BrO ₄ ^- Etc.), halogenated sulfonate ion (FSO) ₃ ^- 、ClSO ₃ ^- Etc.), sulfate ion (CH) ₃ SO ₄ ^- 、CF ₃ SO ₄ ^- 、HSO ₄ ^- Etc.), carbonate ion (HCO) ₃ ^- 、CH ₃ CO ₃ ^- Etc.), aluminate ions (AlCl) ₄ ^- 、AlF ₄ ^- Etc.), hexafluorobismuthate ion (BiF) ₆ ^- ) Carboxylate ion (CH) ₃ COO ^- 、CF ₃ COO ^- 、C ₆ H ₅ COO ^- 、CH ₃ C ₆ H ₄ COO ^- 、C ₆ F ₅ COO ^- 、CF ₃ C ₆ H ₄ COO ^- Etc.), arylborate ion (B (C) ₆ H ₅ ) ₄ ^- 、CH ₃ CH ₂ CH ₂ CH ₂ B(C ₆ H ₅ ) ₃ ^- Etc.), thiocyanate ions (SCN) ^- ) And nitrate ion (NO) ₃ ^- ) And the like.

These anions may have a substituent, and examples of the substituent include an alkyl group, a hydroxyl group, a mercapto group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an arylthio group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, (meth) acryloyloxy group, a hydroxyl (poly) alkyleneoxy group, an amino group, a cyano group, a nitro group, a halogen atom, and the like.

Among these anions, sulfonate anions and carboxylate anions, etc. are preferable.

The onium salt according to one embodiment of the present invention may be a resin containing an acid generator unit in which an anion portion is bonded to a part of a polymer as one embodiment of the photoacid generator (a). Examples of such onium salts include X in the above-mentioned formulae (1), (2), (11) and (12) ^- A resin having a unit represented by the following general formula (5). When the onium salt is contained in the composition as one unit of the resin containing an acid generator unit, the spread of an acid generated upon exposure is suppressed, and therefore LWR can be suppressed, which is preferable.

The unit represented by the general formula (5) may be contained in the resin (B) or may be contained in a resin different from the resin (B).

[ CHEM 17 ]

In the above formula (5), R ¹ And L ¹ Each independently selected from R of formula (1) above ¹ And L ¹ The same selection item.

Z ¹ The alkyl group is a C1-12 linear or branched chain alkyl group, a C1-12 linear or branched chain alkenyl group, and a C6-14 linear or branched chain aryl group. In addition, some or all of the hydrogen atoms of these alkyl groups, alkenyl groups, and aryl groups may be substituted with fluorine atoms. At least 1 methylene group of these groups may be substituted with a divalent heteroatom-containing group.

Examples of the anion portion represented by the above formula (5) include anions shown below. However, the present invention is not limited thereto.

[ CHEM 18 ]

[ CHEM 19 ]

The onium salts according to several embodiments of the present invention preferably have a molar absorption coefficient of less than 1.0X 10 at 365nm ⁵ cm ² Per mol, more preferably less than 1.0X 10 ⁴ cm ² /mol。

Furthermore, the ketone derivative obtained by deprotecting the acetal or thioacetal of an onium salt according to several embodiments of the present invention preferably has a molar absorption coefficient of 1.0X 10 at 365nm ⁵ cm ² More preferably 1.0X 10 mol or more ⁶ cm ² More than mol.

The molar absorption coefficient at 365nm of the ketone derivative is preferably 5 times or more, more preferably 10 times or more, and still more preferably 20 times or more the molar absorption coefficient at 365nm of the onium salt according to the several embodiments of the present invention.

In order to obtain the above characteristics, the onium salt represented by the above formula (1), (2), (11) or (12) may be used.

<2> Process for synthesizing the onium salt

Among the onium salts according to one embodiment of the present invention, a method for synthesizing a sulfonium salt and an iodonium salt will be described. The present invention is not limited thereto.

When the sulfonium group of the aimed sulfonium salt has an alkyl group, the following methods can be mentioned, for example. First, an alkylthio group-containing bromobenzene (in the following formula, h is 1, and an aryl group may have R) is reacted with a Grignard reagent ¹³ Radical) and optionally have R ¹⁴ Benzoyl chloride of the group (in the following formula, i ═ 1) was reacted to obtain an alkylthiobenzophenone derivative. In this case, R may be ¹⁴ The group is a fluoro group or the like, and thereafter an arbitrary substituent is introduced by aromatic nucleophilic substitution reaction to obtain an alkylthiobenzophenone derivative. Is connected withThen, an alkylating agent (R) such as dimethyl sulfate is added ¹² ₂ SO ₄ ) After the formation of the sulfonium salt, salt exchange is performed using a salt having the corresponding anion to obtain a dialkyl-aryl sulfonium salt. Thereafter, an acid catalyst and an alcohol (R) are used ¹⁵ OH) acetalizes the carbonyl group, thereby obtaining the target sulfonium salt.

[ CHEM 20 ]

When the sulfonium group portion of the aimed sulfonium salt has an aryl group, the following methods can be mentioned, for example. First, any R is provided using a Lewis acid ¹⁴ Phenyl (in the following formula, i ═ 1) and bromobenzoyl chloride (in the following formula, h ═ 1, the aryl group may have R ¹³ Base) to obtain the bromobenzophenone derivative. Next, an acid catalyst and an alcohol (R) are used ¹⁵ OH) acetalizing the carbonyl group. Then, a Grignard reagent is used with a compound having R ¹¹ Radical and R ¹² The sulfoxide of the base reacts to obtain sulfonium salt, and the salt with corresponding anion is used for salt exchange to obtain the target sulfonium salt.

[ CHEM 21 ]

In the case of an iodonium salt, the following methods can be mentioned, for example. First, any R is contained using a Lewis acid ¹⁴ Phenyl (in the following formula, m ═ 1) and iodobenzoyl chloride (in the following formula, n ═ 1, and the aryl group may have R ¹³ Base) to obtain the iodobenzophenone derivative. Then, the resulting mixture is reacted with an oxidizing agent such as m-chloroperbenzoic acid (mCPBA) in the presence of an acid such as trifluoromethanesulfonic acid, and then reacted with an aromatic compound R ¹⁷ The reaction of (a) to give an iodonium salt, followed by the use of an acid catalyst and an alcohol (R) ¹⁵ OH) and, if necessary, salt exchange using a salt having a corresponding anion, thereby obtaining the target iodonium salt.

[ CHEM 22 ]

In the case of a polymer component in which an anionic moiety of an onium salt is bonded to a part of a polymer, examples of the synthesis method include the following methods. First, a commercially available or randomly synthesized sulfonate having a polymerizable functional group is salt-exchanged with the above sulfonium salt or iodonium salt to obtain an onium salt (polymerizable onium salt) having a polymerizable functional group in an anionic portion. Next, the obtained polymerizable onium salt is copolymerized with an acid-decomposable compound or the like using a radical initiator, whereby the target polymer component can be obtained.

[ CHEM 23 ]

The target onium salt being mediated by L ³ Examples of the cyclic structure include the following synthetic methods. First, through L ³ Some of the cyclic ketone derivatives (a) forming a cyclic structure are commercially available. The rest can be synthesized at any time. Reacting the cyclic ketone derivative with a compound having R by using a strong acid such as methanesulfonic acid and a dehydrating agent ¹¹ Radical and R ¹² The sulfoxide of the group reacts to obtain a sulfonium salt (in the following formula, the sulfonium group is substituted with R ¹³ Is bonded to an aryl group, but may also be substituted with R ¹⁴ Aryl linkage of (ii). Next, an acid catalyst and an alcohol (R) are used ¹⁵ OH) acetalizes the carbonyl group, whereby the objective sulfonium salt can be obtained.

[ CHEM 24 ]

L of the target onium salt ⁴ Or L ⁵ When the alkenylene group is present, the following synthetic methods can be used, for example. Having R with sodium hydroxide ¹³ Radical or R ¹⁴ Aldol condensation of an acetyl compound (b) and an aldehyde compound (c)Reaction to obtain the unsaturated ketone compound (d). Then, the unsaturated ketone compound is reacted with a compound having R by using a strong acid such as methanesulfonic acid and a dehydrating agent ¹¹ Radical and R ¹² The sulfoxide of the group reacts to obtain a sulfonium salt (in the following formula, the sulfonium group is substituted with R ¹³ Is bonded to an aryl group of (a), but may also be substituted with R ¹⁴ Aryl linkage of (ii). Thereafter, an acid catalyst and an alcohol (R) are used ¹⁵ OH) acetalizes the carbonyl group, whereby the objective sulfonium salt can be obtained.

[ CHEM 25 ]

<3> composition

One embodiment of the present invention relates to a composition containing the photoacid generator (a) and an acid-reactive compound. Preferably the composition further comprises an acid diffusion inhibitor.

(photoacid generators)

The content of the photoacid generator in the composition of one embodiment of the present invention is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 3 to 15 parts by mass, based on 100 parts by mass of the resist composition components other than the photoacid generator.

For the calculation of the content of the photoacid generator described above, the organic solvent is not included in 100 parts by mass of the resist composition components.

When the photoacid generator is contained as 1 unit in a resin, in other words, when the photoacid generator is a polymer component, the portion other than the polymer main chain is taken as a mass basis. When the photoacid generator is a polymer component and is contained as the same polymer unit together with at least 1 unit selected from the group consisting of units represented by the following general formulae (4a) to (4B) (hereinafter, also referred to as "unit C") and units represented by the following general formulae (3a) to (3d) (hereinafter, also referred to as "unit B"), the unit that functions as the photoacid generator (hereinafter, also referred to as "unit a") is preferably 0.1 to 40 mol%, more preferably 1 to 30 mol%, and still more preferably 3 to 20 mol% of all the polymer units.

In the resist composition, the photoacid generator may be used alone or in combination with 2 or more species of photoacid generators, regardless of the polymer component or the low molecular weight component, or may be used in combination with other photoacid generators.

Examples of the photoacid generator other than the one containing the onium salt include general-purpose ionic photoacid generators and nonionic photoacid generators. Examples of the ionic photoacid generator include onium salt compounds other than the above-described onium salts such as iodonium salts and sulfonium salts. Examples of the nonionic photoacid generator include an N-sulfonyloxy imide compound, an oxime sulfonate compound, an organic halogen compound, and a sulfonyldiazomethane compound.

When a photoacid generator other than the one containing the onium salt is contained, the content thereof is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resist composition components other than the total amount of the photoacid generator.

(acid-reactive Compound)

The acid-reactive compound is preferably selected from compounds having a protecting group deprotected by the action of an acid; a compound having a polymerizable group that polymerizes under the action of an acid; and a crosslinking agent having a crosslinking action under the action of an acid; at least any one of.

The compound having a protecting group deprotected by the action of an acid is a compound which is deprotected by the action of an acid to generate a polar group and which has changed solubility in a developer. For example, in the case of aqueous development using an alkaline developer or the like, the following compounds are used: although insoluble in an alkaline developer, the photoacid generator generates an acid upon exposure, and the protecting group is deprotected from the compound in an exposed portion by the action of the generated acid, thereby making the compound soluble in an alkaline developer.

In one embodiment of the present invention, the acid-reactive compound is particularly preferably a resin (B) whose solubility in the developer is changed by the action of an acid.

(resin (B))

The resin (B) contains at least any one of the units B represented by (3a) to (3d) above, which has a protecting group deprotected by the action of an acid.

The unit B has a protecting group deprotected by the action of an acid, and is contained in the resin (B), and the protecting group deprotected by the action of an acid generates a polar group, thereby changing the solubility in a developer. For example, in the case of aqueous development using an alkaline developer or the like, the following compounds are used: although insoluble in an alkaline developer, the photoacid generator generates an acid upon exposure, and the protecting group is deprotected from the unit B in an exposed portion by the action of the generated acid, thereby making the unit B soluble in an alkaline developer.

In the present invention, the alkaline developer is not limited to the alkaline developer, and may be an aqueous neutral developer or an organic solvent developer. Therefore, when an organic solvent developer is used, the compound having a protecting group deprotected by the action of an acid is a compound as follows: the photoacid generator generates an acid upon exposure, and the protective group is deprotected from the compound in the exposed portion by the action of the generated acid to generate a polar group, thereby lowering the solubility in an organic solvent developer.

Examples of the polar group include a hydroxyl group, a carboxyl group, an amino group, and a sulfo group. Among them, a polar group having-OH in the structure is preferable, and a hydroxyl group or a carboxyl group is preferable.

Specific examples of the protecting group deprotected by the action of an acid include groups forming a carboxyl group and a tertiary alkyl ester group; an alkoxy acetal group; a tetrahydropyranyl group; siloxy and benzyloxy, and the like. As the compound having such a protecting group, a compound having a styrene skeleton, a methacrylate skeleton, an acrylate skeleton, or the like, from which such a protecting group is suspended, is preferably used.

The resin (B) may be a low molecular weight compound containing a protecting group instead of the polymer component containing the unit B having a protecting group deprotected by the action of an acid.

The protective group-containing low-molecular-weight compound has at least any one of the units represented by the above (3a) to (3d) in the same manner as the resin (B).

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group, and a part of hydrogen atoms in these groups may be substituted by a halogen. Among them, hydrogen atom, methyl group and trifluoromethyl group are particularly preferable.

In the above general formulae (3a) to (3d), the site represented by the following formula (a-1) or (a-2) is a protecting group (hereinafter, also referred to as "acid labile group") which is deprotected by the action of an acid, and is decomposed by the action of an acid to produce a carboxylic acid or a phenolic hydroxyl group, thereby changing the solubility in a developer.

The broken lines in the following formulae (a-1) and (a-2) represent the sum L in the formulae (3a) to (3d) ¹ Or a bonding portion of an oxygen atom. R in the following formulae (a-1) and (a-2) ² ～R ⁷ Preferably selected from the group consisting of R in the above general formulae (3a) to (3d) ² ～R ⁷ The same selection item.

[ CHEM 26 ]

In the above formula (a-1), R ² And R ³ Each independently is a linear, branched or cyclic alkyl group, and examples thereof include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantan-1-yl group, an adamantan-2-yl group, a norbornan-1-yl group and a norbornan-2-yl group.

R ⁴ Is a linear, branched or cyclic alkyl group which may have a substituent, and the alkyl group is selected from the group consisting of ² The alkyl groups in (b) are each the same option, and a part of the hydrogen atoms thereof may be substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group or the like. R is as defined above ⁵ 、R ⁶ And R ⁷ The ring structure may be formed directly from a single bond or through any one selected from methylene groups.

In the above formula (a-2), R ⁵ And R ⁶ Each independently a hydrogen atom, and a linear or cyclic alkyl group selected from the group consisting of ² Respectively, are the same options.

R ⁷ Is a linear, branched or cyclic alkyl group which may have a substituent, the alkyl group being selected from the group consisting of ² The alkyl groups in (b) are each the same option, and a part of the hydrogen atoms thereof may be substituted with a hydroxyl group, an alkoxy group, a bridging oxygen, an amino group, an alkylamino group or the like. R is as defined above ⁵ 、R ⁶ And R ⁷ The ring structure may be formed directly from a single bond or through any one selected from methylene groups.

Specific examples of the above formulae (a-1) and (a-2) include the following structures. However, the present invention is not limited thereto.

[ CHEM 27 ]

R in the above general formulae (3c) to (3d) ⁸ Is any one selected from the group consisting of an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, an amino group, a cyano group, a nitro group and a halogen atom. They are selected from the group consisting of ¹³ Respectively identical options.

L in the above general formulae (3a) to (3d) ¹ Is a direct bond, a carbonyloxy group, a carbonylamino group, or a linear, branched, cyclic alkylenecarbonyloxy group, alkylenecarbonylamino group which may have a substituent, the carbonyloxy group or the carbonylamino group being bonded to the above-mentioned acid-labile group.

In the formulas (3a) to (3d), l is an integer of 1 to 2, m is an integer of 0 to 4 when l is 1, m is an integer of 0 to 6 when l is 2, n is an integer of 1 to 5 when l is 1, n is an integer of 1 to 7 when l is 2, m + n is 1 to 5 when l is 1, and m + n is 1 to 7 when l is 2.

Specific examples of the unit B represented by the general formulae (3a) to (3d) include the following units. However, the present invention is not limited thereto.

[ CHEM 28 ]

The composition may contain a compound having a polymerizable group which is polymerized by the action of an acid and/or a crosslinking agent having a crosslinking action by the action of an acid, in place of or in addition to the resin (B). The compound having a polymerizable group that polymerizes under the action of an acid is a compound that polymerizes under the action of an acid to change the solubility in a developer. For example, in the case of aqueous development, the polymerization inhibitor acts on a compound soluble in an aqueous developer, and the solubility of the compound in the aqueous developer is reduced after the polymerization. Specifically, compounds having an epoxy group, an ethyleneoxy group, an oxetanyl group, and the like are exemplified.

The compound having a polymerizable group which is polymerized by the action of an acid may be a polymerizable low-molecular compound or a polymer component containing a unit having a polymerizable group.

The crosslinking agent having a crosslinking action under the action of an acid is a compound which is crosslinked under the action of an acid to change the solubility in a developer. For example, in the case of aqueous development, the compound acts on a compound soluble in an aqueous developer, and the solubility of the compound in the aqueous developer is reduced after polymerization or crosslinking. Specifically, there may be mentioned crosslinking agents having a crosslinkable group such as an epoxy group, an ethyleneoxy group, a 1-alkoxyamino group and an oxetanyl group. When the compound is a crosslinking agent having a crosslinking action, examples of the compound to be crosslinked, i.e., a compound which reacts with the crosslinking agent and changes the solubility in a developer include compounds having a phenolic hydroxyl group.

The compound having a crosslinking action by the action of an acid may be a crosslinkable low-molecular compound or a polymer component containing a unit having a crosslinkable group.

The resin (B) may contain, in addition to at least any one of the units B represented by the formulae (3a) to (3d), other units generally used in resist compositions in the polymer component. Examples of the other units include units having at least one skeleton selected from a lactone skeleton, a sultone skeleton, a sulfolane skeleton, a lactam skeleton, and the like; a unit having at least one structure selected from an ether structure, an ester structure, an acetalized structure, a hydroxyl group-containing structure, and the like; a hydroxyaryl-containing unit; and the like. The resin (B) may contain the unit a.

The resin (B) may be contained in the composition as a homopolymer containing the unit B, or as a copolymer having the unit B, the unit a, and at least 1 unit C selected from the general formulae (4a) to (4B) described below. When the resin (B) is a copolymer, the unit B in the resin (B) is preferably 3 to 50 mol%, more preferably 5 to 35 mol%, and still more preferably 7 to 30 mol% of all units of the polymer.

(resin (C))

In one embodiment of the present invention, the composition preferably contains a resin (C) containing 1 or more units C represented by the following formulae (4a) to (4B), or the resin (B) further contains at least one of the units C.

[ CHEM 29 ]

In the above formulae (4a) and (4b), R ¹ 、R ⁸ And L ¹ Each independently selected from R of the above formulae (3a) to (3d) ¹ 、R ⁸ And L ¹ Each of the same options.

R ⁹ Is a compound containing a compound selected from the group consisting of-C (O) -O-, -SO ₂ and-O-SO ₂ -a cyclic group of at least any one of (a), (b), (c), (d), (e) and (d).

p is an integer of 0 to 4, and q is an integer of 1 to 5.

Examples of the cyclic group include those having a lactone skeleton; a sultone backbone; a group of sulfolane skeleton, etc.

The unit C represented by the above formulae (4a) to (4B) may be contained in the copolymer containing the above unit a and/or at least any one of the above formulae (3a) to (3d) as the unit B, or may be a unit of another polymer.

The unit represented by the above formula (4a) is a hydroxyaryl-containing unit (hereinafter, also referred to as "unit C1"), and the unit represented by the above formula (4b) is a compound having a lactone skeleton; a sultone backbone; a unit of a sulfolane skeleton (hereinafter, also referred to as "unit C2").

When a polymer having a hydroxyaryl-containing unit C1 is used, the photoacid generator is preferably used because it can serve as a hydrogen source for decomposition, can further improve the acid generation efficiency, and can have high sensitivity. Further, the polymer having the hydroxyaryl-containing unit C1 is preferably a polymer having a low ionization potential, because secondary electrons are easily generated when an electron beam or Extreme Ultraviolet (EUV) is used as the 1 st active energy ray described later, and the acid generation efficiency of the photoacid generator is improved to thereby achieve high sensitivity.

Examples of the hydroxyaryl-containing unit C1 include the following units. However, the present invention is not limited thereto.

[ CHEM 30 ]

When the hydroxyaryl-containing unit C1 is contained together with at least one selected from the units a and B as a unit of the same polymer, the hydroxyaryl-containing unit C1 is preferably 3 to 90 mol%, more preferably 5 to 80 mol%, and still more preferably 7 to 70 mol% of the total units of the polymer in the application of a positive resist composition for aqueous development. In the negative resist composition for aqueous development, the amount of the polymer is preferably 60 to 99 mol%, more preferably 70 to 98 mol%, and still more preferably 75 to 98 mol% in all units of the polymer.

Contains a lactone skeleton; a sultone backbone; the unit C2 having a sulfolane skeleton is exemplified by the following units. However, the present invention is not limited thereto.

[ CHEM 31 ]

When a sultone skeleton-containing unit or a sulfolane skeleton-containing unit is used as the unit C2, ionization is performed by irradiation of electron beam or Extreme Ultraviolet (EUV) as the 1 st active energy ray to generate an acid, and thus, the deprotection reaction of acetal of an onium salt in several embodiments of the present invention is facilitated, and more ketone derivatives having absorption to the 2 nd active energy ray can be produced. In addition, it is preferable to further change the solubility of the resin in the developer by polarity inversion due to the reaction with the resin (B) containing the unit B, thereby increasing the sensitivity.

A lactone-containing backbone unit as unit C2; a sultone backbone-containing unit; when the unit containing a sulfolane skeleton is contained together with at least one selected from the unit a and the unit B as a unit of the same polymer, the unit C2 is preferably 3 to 70 mol%, more preferably 5 to 50 mol%, and further preferably 7 to 40 mol% in all the units of the polymer.

In the composition according to an embodiment of the present invention, the resin (B) and/or the resin (C) may contain other compounds as units of the same polymer in addition to the unit a, the unit B, and the unit C. The other compound is not particularly limited as long as it is a compound generally used as a resin composition for ArF lithography, KrF lithography, electron beam lithography, EUV lithography, or the like.

(sulfone or sulfonate-containing Low molecular Compound or Polymer)

The composition of one embodiment of the present invention may contain a low molecular compound or polymer containing sulfone or sulfonate.

The sulfone or sulfonate is not particularly limited, and preferably has a linear, branched or cyclic alkyl group; or an aryl group. It is further preferred that a part or all of hydrogen atoms of the alkyl group or the aryl group are substituted with fluorine atoms. By containing this compound, ionization by irradiation of electron beams or extreme ultraviolet rays can be performed to generate an acid, and thus the sensitivity of the resist can be improved.

The content of the sulfone or sulfonate compound is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resist composition components excluding the total amount of the acid generator.

Specific examples of the sulfone or sulfonate-containing compound include dimethyl sulfone, isopropyl methyl sulfone, methyl phenyl sulfone, diphenyl sulfone, phenyl trifluoromethyl sulfone, bis (4-fluorophenyl) sulfone, bis (phenylsulfonyl) methane, methyl methanesulfonate, isopropyl methanesulfonate, ethyl trifluoromethanesulfonate, methyl benzenesulfonate, 1, 3-propane sultone, 1-propene-1, 3-sultone, 1, 4-butane sultone, 1, 2-bis (tosyloxy) ethane, and 1, 8-naphthol sultone, and these may be used alone or in combination of 2 or more.

(Water-repellent fluorine-containing polymer)

The composition according to one embodiment of the present invention may contain a fluorine-containing water-repellent polymer.

The fluorine-containing water-repellent polymer is not particularly limited, and may be a polymer generally used in a liquid immersion exposure process, and preferably has a fluorine atom content higher than that of the polymer. When a resist film is formed using a composition containing a fluorine-containing water-repellent polymer, the fluorine-containing water-repellent polymer can be made non-uniform on the surface of the resist film due to the water repellency of the fluorine-containing water-repellent polymer.

The fluorine content of the water-repellent fluoropolymer is preferably at least 25% of the hydrocarbon-based hydrogen atoms in the water-repellent fluoropolymer are fluorinated, more preferably at least 50%.

The content of the water-repellent polymer in the composition is preferably 0.5 to 10 parts by mass per 100 parts by mass of the polymer (other than the water-repellent polymer) according to one embodiment of the present invention, from the viewpoint of improving the hydrophobicity of the resist film. The water-repellent fluorine polymer may be used alone or in combination of 2 or more.

(photosensitizers and precursors thereof)

The composition of one embodiment of the present invention may contain a photosensitizer and a precursor thereof. Hereinafter, the photosensitizing agent and its precursor have been collectively referred to as "sensitizing compound".

As the above sensitizing compound. The onium salt according to the present invention is not particularly limited as long as the effect of the onium salt is not reduced, and examples thereof include thioxanthone derivatives and acetalized compounds thereof, benzophenone derivatives and acetalized compounds thereof, naphthalene derivatives, anthracene derivatives, and alkyl and aryl alcohols.

The sensitizing compound may contain, for example, a photosensitizer precursor represented by the following general formula (7). The use of the photosensitizer precursor is preferred because the photosensitizer precursor generates a photosensitizer upon irradiation with the 1 st active energy ray, and then a sensitizing reaction occurs between the photosensitizer and the onium salt according to the several embodiments of the present invention upon irradiation with the 2 nd active energy ray, and the sensitivity of the resist can be improved by this sensitizing reaction.

[ CHEM 32 ]

In the above formula (7), Ar ¹¹ And Ar ¹² Each independently is phenylene which may have a substituent, R ²¹ Is any one selected from the group consisting of an alkylthio group, an arylthio group and an alkylthiophenyl group which may have a substituent, W is any one selected from the group consisting of a sulfur atom, an oxygen atom and a direct bond, R ²² Is any of an alkyl group and an aryl group which may have a substituent, each Y is independently any of an oxygen atom and a sulfur atom, R ²³ And R ²⁴ Each independently represents one selected from a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group and aralkyl group which may have a substituent, and R is ²³ And R ²⁴ May be bonded to each other and form a ring structure with 2Y in the formula.

Ar in the above formula (7) ¹¹ And Ar ¹² Are each phenylene, except each R ²¹ Or other than or-W-R ²² May have a substituent (hereinafter, Ar is defined as ¹¹ And Ar ¹² The substituent(s) is (are) described as "substituent(s) 4"). In addition, Ar ¹¹ And Ar ¹² From the aspect of synthesis, it is preferable that the ring is not indirectly bonded.

As at the topExamples of the substituent 4 include an electron donating group. Specific examples of the electron donating group include an alkyl group, an alkenyl group, an alkoxy group, an alkoxyphenyl group, an alkylthio group, an arylthio group, and an alkylthiophenyl group. The substituent 4 may be a substituent having a polyethylene glycol chain (- (CO) ₂ H ₄ ) _n -) long chain alkoxy groups. In addition, the 4 th substituent is bonded to Ar ¹¹ Or Ar ¹² The para-position of (3) may have an OH group as a 4 th substituent.

Note that, in the present invention, Ar ¹¹ Or Ar ¹² The substitution positions such as "para" and the like in the above formula (7) are Y, Ar relative to 2 ¹¹ And Ar ¹² The position of the group to which the bonded quaternary carbon is bonded. The reference to the substitution position such as "para" or the like for other groups, not only the 4 th substituent, but also the position relative to the group bonded to the quaternary carbon is intended.

The alkyl group or alkenyl group as the 4 th substituent is selected from the group consisting of the groups represented by the formula (1) and R ¹¹ The alkyl and alkenyl groups of (1) are the same options. The alkoxy group as the 4 th substituent is selected from the same options as the alkoxy group (-OR) in the 1 st substituent.

Examples of the alkylthio, arylthio and alkylthiophenyl group as the 4 th substituent include the groups R described later ²¹ The alkylthio group, the arylthio group and the alkylthiophenyl group of (A) are the same groups.

Any methylene group of the above alkyl groups in the 4 th substituent may be substituted with a-C (═ O) -group or a-O-C (═ O) -group. In which the radicals-C (═ O) -and-O-C (═ O) -are preferably not bound to Ar in the abovementioned 4 substituents ¹¹ And Ar ¹² A direct bond and. In the substituent 4, it is preferable that the continuous bonding of hetero atoms such as-O-O, -S-and-S-O-is not present.

When the 4 th substituent is alkoxy, alkoxyphenyl, alkylthio, arylthio and alkylthiophenyl, it is preferably reacted with Ar as the substituent ¹¹ And Ar ¹² Ortho-and/or para-bonding of the phenylene group(s). In this case, the number of substituents is preferably 3 or less.

As R in the above formula (7) ²¹ Is selected from the group consisting of alkylthio, arylthio and alkylthiophenyl which may have a substituentAny of the above.

As R ²¹ The alkylthio group of (2) is preferably an alkylthio group having 1 to 20 carbon atoms such as a methylthio group, an ethylthio group, an n-propylthio group, an n-butylthio group and the like, and more preferably an alkylthio group having 1 to 12 carbon atoms.

As R ²¹ Specific examples of the arylthio group of (b) include phenylthio group and naphthylthio group.

As R ²¹ Specific examples of the alkylthiophenyl group of (3) include a phenyl group to which an alkylthio group having 1 to 20 carbon atoms is bonded such as a methylthiophenyl group, an ethylthiophenyl group, a propylthiophenyl group and a butylthiophenyl group, and a phenyl group to which an alkylthio group having 1 to 12 carbon atoms is bonded is more preferable. As R ²¹ The substitution position of the alkylthio group bonded to the phenylene group in (A) is not particularly limited, and the para-position is preferable from the viewpoint of improving electron donating property and molar absorption coefficient of 365 nm. R is as defined above ²¹ Preferably bonded to as Ar ¹¹ Ortho or para to the phenylene group of (a).

As R in the above formula (7) ²² Any one of an alkyl group and an aryl group which may have a substituent, selected from the group consisting of the above-mentioned R ¹¹ Respectively identical options.

R in the above formula (7) ²¹ And R ²² May have a substituent as the substituent (hereinafter, R is represented ²¹ And R ²² The substituent(s) of (3) is (are) referred to as "5 th substituent"), and is not particularly limited, and examples thereof include, in addition to the above-mentioned 4 th substituent, electron-withdrawing groups and the like. Examples of the electron-withdrawing group include a nitro group and a sulfonyl group. Or R may be substituted with R ²¹ Or R ²² In the above-mentioned polymer, a polymerizable group is introduced and polymerized to give a sensitizing effect, and the 5 th substituent may be a structure containing a main chain of the polymer. Examples of the polymerizable group include a (meth) acryloyloxy group, an epoxy group, and a vinyl group.

When W in the formula (7) is an oxygen atom or a sulfur atom, W is preferably Ar ¹² Ortho or para. When W is a direct bond, W is preferably Ar ¹² Ortho or para.

R in the above formula (7) ²¹ Total carbon atoms ofThe number is not particularly limited, R ²¹ When the substituent(s) are present, the total number of carbon atoms is preferably 1 to 20. R in the above formula (7) ²² The total number of carbon atoms of (2) is not particularly limited, R ²² When the substituent(s) are present, the total number of carbon atoms is preferably 1 to 20.

When the photosensitizer precursor is a polymer, R is not a moiety containing a polymer main chain which is a 5 th substituent ²¹ And R ²² The total number of carbon atoms of (A) is preferably 1 to 20.

Each Y is independently any one of an oxygen atom and a sulfur atom.

R ²³ And R ²⁴ Each independently is any one selected from linear, branched or cyclic alkyl, alkenyl and alkynyl groups, and aralkyl groups which may have a substituent. As R ²³ And R ²⁴ Alkyl and alkenyl selected from the group consisting of R in the above formula (1) ¹¹ The same options are given for alkyl and alkenyl groups of (a).

As R ²³ And R ²⁴ Is selected from the group consisting of R ²³ And R ²⁴ A part of the alkyl group of (b) becomes a triple-bonded group. As R ²³ And R ⁴ Selected from the above R ²³ And R ²⁴ A group in which a part of hydrogen of the alkyl group in (1) is substituted with an aryl group such as phenyl or naphthyl.

R in the above formula (7) ²³ And R ²⁴ May have a substituent (hereinafter, R is represented by ²³ And R ²⁴ The substituent(s) is (are) described as "substituent(s) 6"), and there are no particular limitations thereon, and examples thereof include, in addition to the substituent(s) 5, aryl groups such as phenyl and naphthyl.

R in the above formula (7) ²³ And R ²⁴ The total number of carbon atoms of (A) is not particularly limited, and the photosensitizer precursor may be a constituent of a polymer, but R is a group represented by ²³ Or R ²⁴ When the substituent(s) are present, the total number of carbon atoms is preferably 1 to 20.

R is as defined above ²³ And R ²⁴ May be bonded to each other to form a ring structure with 2Y in the formula.

That is, the photosensitizer precursor according to one embodiment of the present invention is represented by the following formula (8)Shown in the figure. In the following formula (8) — R ²⁵ -R ²⁶ -is preferably- (CH) ₂ ) _n And n is an integer of 2 or more. n is not particularly limited as long as it is 2 or more, but is preferably 8 or less from the viewpoint of ease of synthesis. R ²⁵ And R ²⁶ And R in the above formula (7) ²³ And R ²⁴ The structures bonded to each other to form rings correspond to each other.

[ CHEM 33 ]

In the above formula (8), R ²⁵ And R ²⁶ May have the same general formula as R ²³ And R ²⁴ The same substituent as the above substituent No. 6. May be directed to the above R ²³ Or R ²⁴ In which a polymerizable group is introduced and polymerized, is used as a polymer to which a sensitizing effect is imparted.

In addition, R is ²³ And R ²⁴ The total number of carbon atoms of (A) is preferably 1 to 20. When the photosensitizer precursor is a polymer, R is preferably contained in a portion other than the polymer main chain portion which is the 6 th substituent ²³ And R ²⁴ The total number of carbon atoms of (2) is 1 to 20.

The molar absorptivity at 365nm of the sensitizer formed by the acid-treated sensitizer precursor, i.e., the sensitizer having a carbonyl group formed when the sensitizer precursor is deprotected by the action of an acid, is preferably 1.0X 10 ⁵ cm ² More than mol. Preferably, the molar absorptivity at 365nm is high, but 1.0X 10 ¹⁰ cm ² The value is actually not more than mol. In order to set the molar absorption coefficient within the above range, the photosensitizer precursor may contain, for example, 1 or more alkylthio groups, arylthio groups, alkylthiophenyl groups, or 2 or more alkoxy or aryloxy groups.

In the present invention, the molar absorptivity is a molar absorptivity of 365nm measured by a UV-VIS absorptometer using chloroform as a solvent.

In view of ease of synthesis and light absorption characteristics, one embodiment of the present invention relates toThe photosensitizer precursor is preferably in the entirety of the photosensitizer precursor, -Y-R ²³ and-Y-R ²⁴ or-Y-R ²⁵ -R ²⁶ -Y-is 4 or less of the groups other than alkylthio, arylthio, alkoxyphenyl, alkylthiophenyl, alkoxy and aryloxy.

As the photosensitizer precursor represented by the above formula (7) or formula (8), the following photosensitizer precursors can be exemplified. In the following examples, the parenthesized parts represent polymer units. The photosensitizer precursor in the several embodiments of the present invention is not limited thereto.

[ CHEM 34 ]

[ CHEM 35 ]

[ CHEM 36 ]

A method for synthesizing a photosensitizer precursor according to one embodiment of the present invention will be described. The invention is not limited thereto.

When the photosensitizer precursor according to one embodiment of the present invention has a structure represented by the following formula (9), it can be synthesized, for example, by the following method. First, a compound selected from the group consisting of compounds having-W-R ²² 1 of alkoxybenzoyl chloride, alkylbenzoyl chloride, thioalkoxybenzoyl chloride and thioalkylbenzoyl chloride of the group, and substances in which the alkyl group of these substances becomes an aryl group; and has R ²¹ The halogenated benzene of the base group is subjected to Grignard reaction to obtain the benzophenone derivative. Next, a benzophenone derivative, an alcohol and, if necessary, a trialkyl orthoformate (R) as a dehydrating agent are added ²³ 、R ²⁴ Alkyl) at 0 ℃ to reflux temperature for 1 to 120 hoursThereby, a derivative represented by the following formula (9) can be obtained.

[ CHEM 37 ]

(other Components)

In the composition of one embodiment of the present invention, an optional component may be combined as necessary in addition to the above components. The optional components include an acid diffusion controller, a surfactant, an organic carboxylic acid, an organic solvent, a dissolution inhibitor, a stabilizer, a dye, and a polymer other than those described above, which are used in a general resist composition.

The acid diffusion controller described above can exert the effect of suppressing the diffusion phenomenon of the acid generated from the photoacid generator in the resist film, and suppressing an undesirable chemical reaction in the non-exposed region. Therefore, the storage stability of the obtained resist composition can be further improved, the resolution as a resist can be further improved, and the variation in line width of the resist pattern due to the variation in the shelf life from exposure to development treatment can be suppressed, thereby obtaining a resist composition excellent in process stability.

Examples of the acid diffusion controlling agent include a compound having 1 nitrogen atom, a compound having 2 nitrogen atoms, and a compound having 3 nitrogen atoms in the same molecule; an amide group-containing compound; a urea compound; nitrogen-containing heterocyclic compounds, and the like. Further, as the acid diffusion controller, a photodegradable base which generates a weak acid by exposure to light can be used. Examples of the photodegradable base include onium salt compounds and iodonium salt compounds which exhibit acid diffusion controllability due to decomposition by exposure to light.

Specific examples of the acid diffusion controlling agent include compounds described in japanese patent No. 3577743, japanese patent No. 2001-.

The content of the acid diffusion controller is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and still more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the resist composition component.

The above surfactant is preferably used to improve coatability. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl esters, polyoxyethylene polyoxypropylene block copolymers, nonionic surfactants such as sorbitol fatty acid esters and polyoxyethylene sorbitol fatty acid esters, fluorine surfactants, organosiloxane polymers, and the like.

The content of the surfactant is preferably 0.0001 to 2 parts by mass, and more preferably 0.0005 to 1 part by mass, per 100 parts by mass of the resist composition component.

Examples of the organic carboxylic acid include aliphatic carboxylic acids, alicyclic carboxylic acids, unsaturated aliphatic carboxylic acids, hydroxycarboxylic acids, alkoxycarboxylic acids, ketocarboxylic acids, benzoic acid derivatives, phthalic acid, terephthalic acid, isophthalic acid, 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, and 2-hydroxy-3-naphthoic acid. Since the electron beam exposure under vacuum may volatilize from the resist film surface to contaminate the inside of the drawing chamber, the preferred organic carboxylic acid is an aromatic organic carboxylic acid, and among them, benzoic acid, 1-hydroxy-2-naphthoic acid, and 2-hydroxy-3-naphthoic acid are preferred.

The content of the organic carboxylic acid is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.01 to 3 parts by mass, based on 100 parts by mass of the resist composition component.

As the organic solvent, for example, ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, Propylene Glycol Monomethyl Ether (PGME), Propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl β -methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone alcohol, N-methylpyrrolidone, N-dimethylformamide, γ -butyrolactone, N-dimethylacetamide, propylene carbonate, ethylene carbonate, and the like are preferable. These organic solvents may be used alone or in combination.

The resist composition component solvent is dissolved in the solvent at a solid content concentration of preferably 1 to 40 mass%. More preferably 1 to 30% by mass, and still more preferably 3 to 20% by mass. By setting the solid content concentration in such a range, the film thickness can be realized.

When the resist composition according to one embodiment of the present invention contains a polymer, the polymer preferably has a weight average molecular weight of 2000 to 200000, more preferably 2000 to 50000, and still more preferably 2000 to 15000. The polymer preferably has a dispersity (molecular weight distribution) (Mw/Mn) of 1.0 to 1.7, more preferably 1.0 to 1.2, from the viewpoint of sensitivity. The weight average molecular weight and the degree of dispersion of the above-mentioned polymer are defined as polystyrene equivalent values determined based on GPC.

The composition of one embodiment of the present invention is obtained by mixing the components of the composition, and the mixing method is not particularly limited.

<4> method for manufacturing device

One embodiment of the present invention is a method for manufacturing a device, including the steps of: a step of forming a resist film by applying the composition to a substrate or the like; irradiating the resist film with a 1 st active energy ray; irradiating the resist film irradiated with the 1 st active energy ray with a 2 nd active energy ray; and a step of obtaining a pattern by developing the resist film after the irradiation with the 2 nd active energy ray.

One embodiment of the present invention may be a method for manufacturing a substrate having a pattern before a chip is singulated. The method comprises the following steps: a step of forming a resist film using the composition; irradiating the first active energy ray with the first active energy ray; irradiating the second active energy ray with the second active energy ray; and a step of forming a pattern.

One embodiment of the present invention may be a method for manufacturing a device, including the steps of: a step of forming a coating film on a substrate using the composition; and a step of exposing the coating film to light using a 1 st active energy ray and a 2 nd active energy ray to obtain an interlayer insulating film.

The onium salt according to the present invention is not particularly limited as long as it does not significantly absorb the 2 nd active energy line as the 1 st active energy line and the 2 nd active energy line, and it is preferable that the 1 st active energy line has a shorter wavelength than the 2 nd active energy line or that the energy of a photon or a particle beam is higher than the 2 nd active energy line. The following examples illustrate each active energy line, but the present invention is not limited thereto as long as the 1 st active energy line has a shorter wavelength than the 2 nd active energy line or the energy of the photon or particle beam is higher than the 2 nd active energy line.

The 1 st active energy ray is not particularly limited as long as it can generate an active species such as an acid in the resist film after irradiation of the resist film, and examples thereof include a KrF excimer laser, an ArF excimer laser, an electron beam, and Extreme Ultraviolet (EUV).

The 2 nd active energy ray may be the following energy ray. That is, after the irradiation with the 1 st active energy ray, an acid is generated in the resist film, and the acetal or thioacetal moiety of the onium salt according to the several embodiments of the present invention is deprotected by the action of the generated acid to generate a ketone derivative, and the ketone derivative is activated by the energy ray to generate an active species such as an acid. For example, the light refers to KrF excimer laser, UV, visible light, and the like, and particularly, light in the 365nm (i-ray) to 436nm (g-ray) region of UV light is preferably used.

The substrate is not particularly limited, and a known substrate can be used. Examples thereof include substrates made of metals such as silicon, silicon nitride, titanium, tantalum, palladium, copper, chromium, and aluminum; glass substrates, and the like.

In one embodiment of the present invention, the active energy ray used for exposure in the photolithography step employed for obtaining an interlayer insulating film or the like for manufacturing an LSI is preferably UV, KrF excimer laser, ArF excimer laser, electron beam, Extreme Ultraviolet (EUV), or the like.

The irradiation amount of the 1 st active energy ray varies depending on the kind and mixing ratio of each component in the photocurable composition, the thickness of the coating film, and the like, but is preferably 1J/cm ² Below or 1000 uC/cm ² The following.

In one embodiment of the present invention, the resist film formed from the resist composition preferably has a film thickness of 10 to 200 nm. The resist composition is applied to a substrate by a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, and prebaked at 60 to 150 ℃ for 1 to 20 minutes, preferably at 80 to 120 ℃ for 1 to 10 minutes to form a thin film. The film thickness of the coating film is 5 to 200nm, preferably 10 to 100 nm.

Examples

The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to these examples.

<1> Synthesis of sulfonium salt

< Synthesis of sulfonium salt 1>

(Synthesis example 1) Synthesis of 4-fluoro-4' -methylthiobenzophenone

8.0g of 4-bromothioanisole was dissolved in 32g of tetrahydrofuran, and 39ml of a 1mol/L THF solution of methylmagnesium bromide was added dropwise thereto at a temperature of 5 ℃ or lower. After the dropwise addition, the mixture was stirred at 35 ℃ for 30 minutes to obtain a THF solution of 4-methylthiophenylmagnesium bromide. 7.0g of 4-fluorobenzoyl chloride was dissolved in THF15g, and a THF solution of 4-methylthiophenylmagnesium bromide was added dropwise to the resulting solution at 10 ℃ or lower, followed by stirring at 25 ℃ for 1 hour. After stirring, 50g of a 10% by mass aqueous ammonium chloride solution was added thereto at 20 ℃ or lower and further stirred for 10 minutes, and the organic layer was extracted with 80g of ethyl acetate. The crude crystals were obtained by washing with water and then distilling off ethyl acetate and tetrahydrofuran. The crude crystals were recrystallized from 120g of ethanol to give 6.1g of 4-fluoro-4' -methylthiobenzophenone.

[ CHEM 38 ]

Synthesis example 2 Synthesis of 4-methylthio-4' -phenylthiobenzophenone

6.0g of 4-fluoro-4' -methylthiobenzophenone obtained in Synthesis example 1 was dissolved in DMF30g, and 3.2g of thiophenol and 4.0g of potassium carbonate were added thereto, followed by stirring at 70 ℃ for 4 hours. After stirring, 90g of pure water was added thereto and stirred for another 10 minutes, and the organic layer was extracted with 60g of toluene. After washing with water for 3 times, toluene was distilled off to obtain crude crystals. The crude crystals were recrystallized from 40g of ethanol to give 5.6g of 4-methylthio-4' -phenylthiobenzophenone.

[ CHEM 39 ]

Synthesis example 3 Synthesis of dimethyl- [4- (4-phenylthio) benzoylphenyl ] sulfonium-nonafluorobutane sulfonate

3.0g of 4-methylthio-4' -phenylthiobenzophenone obtained in Synthesis example 2 was dissolved in 20g of acetonitrile, and 2.8g of dimethyl sulfate was added thereto, followed by stirring at 70 ℃ for 4 hours. After stirring, 60g of pure water was added thereto, followed by stirring for 10 minutes, and then 40g of toluene was added thereto, followed by washing. To the aqueous layer obtained were added 3.0g of potassium nonafluorobutane sulfonate and 30g of methylene chloride, and the mixture was stirred for about 1 hour. The resulting solution was separated and washed with water 3 times, and then dichloromethane was distilled off to obtain a crude crystal. The crude crystal was purified by silica gel column chromatography (dichloromethane/methanol 90/10 (vol.)) to give 4.9g of dimethyl- [4- (4-phenylthio) benzoylphenyl ] sulfonium-nonafluorobutane sulfonate.

[ CHEM 40 ]

Synthesis example 4 Synthesis of {4- [ dimethoxy- (4-phenylthiophenyl) methyl ] phenyl } dimethylsulfonium nonafluorobutanesulfonate (sulfonium salt 1)

1.0g of dimethyl- [4- (4-phenylthio) benzoylphenyl ] sulfonium-nonafluorobutane sulfonate obtained in Synthesis example 3 was dissolved in 2.5g of methanol, and 1.0g of trimethyl orthoformate and 4.0mg of concentrated sulfuric acid were added thereto, followed by stirring at 60 ℃ for 2 hours. After stirring, the reaction solution was added to a mixed solution of 30g of methylene chloride and 10g of a 3 mass% aqueous sodium bicarbonate solution, and the mixture was stirred for 10 minutes to recover an organic layer. The obtained organic layer was washed with water 3 times, and methylene chloride was distilled off to obtain 1.0g of {4- [ dimethoxy- (4-phenylthiophenyl) methyl ] phenyl } dimethylsulfonium-nonafluorobutanesulfonate.

[ CHEM 41 ]

< Synthesis of sulfonium salt 2>

Synthesis example 5 Synthesis of {4- [ diethoxy- (4-phenylthiophenyl) methyl ] phenyl } dimethylsulfonium-nonafluorobutanesulfonate (sulfonium salt 2)

The same procedures as in Synthesis example 4 above were carried out except for using ethanol instead of methanol and triethyl orthoformate instead of trimethyl orthoformate to obtain 1.2g of {4- [ diethoxy- (4-phenylthiophenyl) methyl ] phenyl } dimethylsulfonium-nonafluorobutanesulfonate.

[ CHEM 42 ]

< Synthesis of sulfonium salt 3>

Synthesis example 6 Synthesis of Ethyl- [4- (4-phenylthiobenzoyl) phenyl ] methylsulfinium-4- (3-hydroxyadamantylcarbonyloxy) -1,1, 2-trifluorobutanesulfonate

Ethyl- [4- (4-phenylthiobenzoyl) phenyl ] was obtained in the same manner as in Synthesis example 3, except that diethyl sulfate was used in place of dimethyl sulfate and sodium 4- (3-hydroxyadamantylcarbonyloxy) -1,1, 2-trifluorobutane sulfonate was used in place of potassium nonafluorobutane sulfonate]5.1g of methylsulfonium-4- (3-hydroxyadamantylcarbonyloxy) -1,1, 2-trifluorobutane sulfonate. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁶ cm ² More than mol.

[ CHEM 43 ]

Synthesis example 7 Synthesis of {4- [ dimethoxy- (4-phenylthiophenyl) methyl ] phenyl } ethylmethylsulfonium-4- (3-hydroxyadamantylcarbonyloxy) -1,1, 2-trifluorobutanesulfonate salt (sulfonium salt 3)

Using ethyl- [4- (4-phenylthiobenzoyl) phenyl]Methyl sulfonium-4- (3-hydroxyadamantylcarbonyloxy) -1,1, 2-trifluorobutane sulfonate instead of {4- [ dimethoxy- (4-thiophenylphenyl) methyl]Synthesis example 4 was repeated in the same manner with the exception of phenyl } dimethylsulfonium nonafluorobutane sulfonate to give {4- [ dimethoxy- (4-phenylthiophenyl) methyl group]Phenyl } ethylmethylsulfonium-4- (3-hydroxyadamantylcarbonyloxy) -1,1, 2-trifluorobutanesulfonate 1.1 g. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol, with ethylmethyl- [4- (4-phenylthio-benzoyl) phenyl ] obtained in Synthesis example 6]The molar absorptivity of sulfonium-4- (3-hydroxyadamantylcarbonyloxy) -1,1, 2-trifluorobutane sulfonate at 365nm is less than 1/10.

[ CHEM 44 ]

< Synthesis of sulfonium salt 4>

(Synthesis example 8) Synthesis of 4-methylthio-4' - (4-methoxyphenylthio) benzophenone

The same procedures as in Synthesis example 2 above were repeated except for using 4-methoxyphenylphenol instead of thiophenol to give 4.6g of 4-methylthio-4' - (4-methoxyphenylthio) benzophenone.

[ CHEM 45 ]

(Synthesis example 9) Synthesis of {4- [4- (4-methoxyphenylthio) benzoyl ] phenyl } -dimethyl-sulfonium-camphorsulfonate

The same procedures as in Synthesis example 3 above were repeated except for using 4-methylthio-4 '- (4-methoxyphenylthio) benzophenone instead of 4-methylthio-4' -phenylthio benzophenone and using (. + -.) -10-camphorsulfonic acid sodium salt instead of potassium nonafluorobutane sulfonate to obtain dimethyl- {4- [4- (4-methoxyphenylthio) benzoyl ] benzophenone]Phenyl } sulfonium-camphorsulfonic acidAcid salt 4.3 g. The molar absorption coefficient at 365nm of the obtained compound was 3.0X 10 ⁶ cm ² More than mol.

[ CHEM 46 ]

Synthesis example 10 Synthesis of {4- { dimethoxy- [4- (4-methoxyphenylthio) phenyl ] methyl } phenyl } dimethylsulfonium-camphorsulfonate (sulfonium salt 4)

Dimethyl- {4- [4- (4-methoxyphenylthio) benzoyl]1.0g of phenyl } sulfonium-camphorsulfonate was dissolved in 2.5g of methanol, and 1.0g of trimethyl orthoformate and 50mg of (. + -.) -10-camphorsulfonic acid were added thereto, followed by stirring at 60 ℃ for 6 hours. After stirring, the reaction solution was added to a mixed solution of 30g of methylene chloride and 10g of a 3 mass% aqueous sodium bicarbonate solution, and stirred for 10 minutes, thereby recovering an organic layer. The obtained organic layer was washed with water 3 times, and methylene chloride was distilled off to obtain {4- { dimethoxy- [4- (4-methoxyphenylthio) phenyl group]Methyl phenyl dimethyl sulfonium camphorsulfonate 1.0 g. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol, and the same as that of dimethyl- {4- [4- (4-methoxyphenylthio) benzoyl group obtained in Synthesis example 9]The molar absorptivity at 365nm is less than 1/10 in comparison with that of phenyl } -sulfonium-camphorsulfonate.

[ CHEM 47 ]

< Synthesis of sulfonium salt 5 >

(Synthesis example 11) Synthesis of 2-thiophenylbenzoic acid

9.2g of 2-mercaptobenzoic acid was dissolved in DMF60g, and 9.4g of bromobenzene, 10g of potassium carbonate and 6.0g of cuprous chloride were added thereto, followed by stirring at 90 ℃ for 6 hours. After stirring, 180g of pure water was added thereto and the mixture was stirred for another 10 minutes, and the organic layer was extracted with 120g of methylene chloride. After washing with water 3 times, dichloromethane was distilled off to obtain crude crystals. The crude crystals were recrystallized from 80g of ethanol to give 10.6g of 2-thiophenylbenzoic acid.

[ CHEM 48 ]

(Synthesis example 12) Synthesis of 2-phenylthiobenzoyl chloride

To 10.0g of 2-phenylthiophenylbenzoic acid obtained in Synthesis example 11 was added 60g of thionyl chloride, and the mixture was stirred at 60 ℃ for 4 hours. After stirring, thionyl chloride was distilled off under reduced pressure to obtain 10.8g of 2-phenylthiobenzoyl chloride.

[ CHEM 49 ]

(Synthesis example 13) Synthesis of 4-methylthio-2' -phenylthiobenzophenone

The same procedures as in Synthesis example 1 above were repeated except for using 2-phenylthiobenzoyl chloride instead of 4-fluorobenzoyl chloride to give 6.5g of 4-methylthio-2' -phenylthiobenzophenone.

[ CHEM 50 ]

Synthesis example 14 Synthesis of dimethyl- [4- (2-phenylthiobenzoyl) phenyl ] sulfonium-methylsulfate

3.0g of 4-methylthio-2' -phenylthiobenzophenone was dissolved in 10g of acetonitrile, and 2.8g of dimethyl sulfate was added thereto, followed by stirring at 70 ℃ for 4 hours. After stirring, the reaction solution was added dropwise to 40g of ethyl acetate to precipitate a solid. The solid was filtered off, washed with 10g of ethyl acetate and dried to give dimethyl- [4- (2-phenylthiobenzoyl) phenyl ] methyl acetate]Sulfonium-methyl sulfate 4.1 g. The molar absorption coefficient at 365nm of the obtained compound was 5.0X 10 ⁵ cm ² More than mol.

[ CHEM 51 ]

Synthesis example 15 Synthesis of {4- [ dimethoxy- (2-phenylthiophenyl) methyl ] phenyl } dimethylsulfonium-benzoate (sulfonium salt 5)

Dimethyl- [4- (2-phenylthio-benzoyl) phenyl ] obtained in Synthesis example 14]3.0g of sulfonium-methylsulfate was dissolved in 7.5g of methanol, and 3.0g of trimethyl orthoformate and 12.0mg of concentrated sulfuric acid were added thereto, followed by stirring at 60 ℃ for 2 hours. After stirring, the reaction solution was dropped into 30g of a 3 mass% aqueous sodium hydrogencarbonate solution. Thereafter, 30g of methylene chloride and 3.0g of sodium benzoate were added thereto, and the mixture was stirred for 3 hours. After stirring, the organic layer was separated and recovered, washed with water for 3 times, and then dichloromethane was distilled off to obtain coarse crystals. The crude crystal was purified by silica gel column chromatography (dichloromethane/methanol 90/10 (vol.); 0.1% by mass of triethylamine was added) to give {4- [ dimethoxy- (2-phenylthiophenyl) methyl group]Phenyl } dimethylsulfonium-benzoate 1.2 g. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than/mol, with dimethyl- [4- (2-thiophenyl-benzoyl) phenyl ] obtained in Synthesis example 14]The sulfonium-methylsulfate has a molar absorption coefficient of less than 1/5 at 365 nm.

[ CHEM 52 ]

< Synthesis of sulfonium salt 6 >

Synthesis example 16 Synthesis of 2, 4-dimethoxy-4' -fluorobenzophenone

3.0g of aluminum chloride was added to 28g of methylene chloride, and the temperature was adjusted to 0 ℃. To this was added 3.0g of 2, 4-dimethoxybenzene, and 3.4g of 4-fluorobenzoyl chloride was dissolved in 6.8g of dichloromethane and added dropwise over 30 minutes. After dropwise addition, the mixture was stirred at 25 ℃ for 1 hour, 60g of pure water was added thereto, and the mixture was further stirred for 5 minutes, followed by extraction with 20g of toluene 2 times. After the liquid separation, the solvent of the obtained organic layer was distilled off. The obtained residue was recrystallized from 30g of ethanol to conduct purification, to obtain 5.2g of 2, 4-dimethoxy-4' -fluorobenzophenone.

[ CHEM 53 ]

Synthesis example 17 Synthesis of 2, 4-dimethoxy-4' - (n-propylthio) benzophenone

5.0g of 2, 4-dimethoxy-4' -fluorobenzophenone obtained in Synthesis example 16 was dissolved in DMF30g, and 1.6g of 1-propanethiol and 3.2g of potassium carbonate were added thereto, followed by stirring at 70 ℃ for 4 hours. After stirring, 90g of pure water was added thereto and stirred for another 10 minutes, and the organic layer was extracted with 60g of toluene. After washing with water 3 times, toluene was distilled off to give a crude product. Purification by silica gel column chromatography (hexane/ethyl acetate 75/25 (vol.)) gave 4.8g of 2, 4-dimethoxy-4' - (n-propylthio) benzophenone.

[ CHEM 54 ]

Synthesis example 18 Synthesis of [4- (2, 4-Dimethoxybenzoyl) phenyl ] ethyl-n-propylsulfonium-nonafluorobutane sulfonate

Synthesis example 3 was repeated in the same manner with the exception that 2, 4-dimethoxy-4 '- (n-propylthio) benzophenone was used in place of 4-methylthio-4' -phenylthiobenzophenone and diethyl sulfate was used in place of dimethyl sulfate to obtain [4- (2, 4-dimethoxybenzoyl) phenyl group]Ethyl-n-propylsulfonium-nonafluorobutane sulfonate 5.0 g. The molar absorption coefficient at 365nm of the obtained compound was 5.0X 10 ⁵ cm ² More than mol.

[ CHEM 55 ]

Synthesis example 19 Synthesis of {4- [ (2, 4-dimethoxyphenyl) -dimethoxy-methyl ] phenyl } ethyl-n-propylsulfonium-nonafluorobutanesulfonate (sulfonium salt 6)

Using [4- (2, 4-dimethoxybenzoyl) phenyl]Ethyl-n-propylsulfonium-nonafluorobutanesulfonate instead of dimethyl- [4- (4-phenylthiobenzoyl) phenyl]In the same manner as in Synthesis example 4 except for sulfonium-nonafluorobutanesulfonate, {4- [ (2, 4-dimethoxyphenyl) dimethoxymethyl group was obtained]Phenyl } ethyl-n-propylsulfonium-nonafluorobutane sulfonate 5.1 g. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² (iv) less than mol, and a molar absorption coefficient at 365nm of less than 5 min 1 compared with {4- (2, 4-dimethoxybenzoyl) phenyl } ethyl-n-propylsulfonium-nonafluorobutane sulfonate obtained in Synthesis example 18.

[ CHEM 56 ]

< Synthesis of sulfonium salt 7 >

(Synthesis example 20) Synthesis of 4-bromo-4' -phenylthiobenzophenone

3.0g of aluminum chloride was added to 28g of methylene chloride to adjust the temperature to 0 ℃. After 4.0g of diphenyl sulfide was added thereto, 3.4g of 4-bromobenzoyl chloride was dissolved in 6.8g of methylene chloride and added dropwise over 30 minutes. After dropwise addition, the mixture was stirred at 25 ℃ for 1 hour, 60g of pure water was added thereto, and the mixture was further stirred for 5 minutes, followed by washing with 20g of toluene 2 times. The organic layer was separated, and the solvent was distilled off. The obtained residue was recrystallized from isopropyl alcohol to purify it, to obtain 5.2g of 4-bromo-4' -phenylthiobenzophenone.

[ CHEM 57 ]

Synthesis example 21 Synthesis of 4-bromo-4' -phenylthiobenzophenone dimethyl acetal

5.0g of 4-bromo-4' -phenylthiobenzophenone obtained in Synthesis example 20 above was dissolved in 30g of methanol, and trimethyl orthoformate 5.0g and concentrated sulfuric acid 30mg were added thereto, followed by stirring at 60 ℃ for 4 hours. After the stirring, 150g of 3 mass% sodium bicarbonate water was added, and the mixture was further stirred for 10 minutes to precipitate a solid. The precipitated solid was filtered and redissolved in 30g of methylene chloride. After washing with water 3 times, methylene chloride was distilled off to obtain 5.0g of 4-bromo-4' -phenylthiobenzophenone dimethyl acetal.

[ CHEM 58 ]

Synthesis example 22 Synthesis of {4- [ dimethoxy- (4-phenylthiophenyl) methyl ] phenyl } diphenylsulfonium-nonafluorobutanesulfonate (sulfonium salt 7)

2.0g of tetrahydrofuran, 0.4g of magnesium and 1, 2-dibromoethane were added to the flask dried in advance to activate magnesium. After the activation was confirmed, the temperature of the solution was raised to 50 ℃ and 4.0g of 4-bromo-4' -phenylthiobenzophenone dimethyl acetal obtained in Synthesis example 20 above was dissolved in 6.0g of THF6.0g of the solution. After dropwise addition, stirring at 50 ℃ for 5h to give 4- [ dimethoxy- (4-phenylthiophenyl) methyl]Phenylmagnesium bromide in THF. Dissolving 1.9g of diphenylsulfoxide, 1.8g of trimethylchlorosilane and 0.8g of triethylamine in 9.5g of dichloromethane, and dropwise adding 4- [ dimethoxy- (4-phenylthiophenyl) methyl group to the solution at 10 ℃ or lower]A THF solution of phenylmagnesium bromide, followed by stirring at 25 ℃ for 1 hour. After stirring, 30g of a 10 mass% aqueous ammonium chloride solution was added at 5 ℃ or lower, followed by stirring for 10 minutes and washing with 5.0g of isopropyl ether for 2 times. Thereafter, 40g of methylene chloride and 3.1g of potassium nonafluorobutane sulfonate were added, and the mixture was stirred at 25 ℃ for about 2 hours. After washing with water for 3 times, dichloromethane was distilled off to obtain a crude crystal. The crude crystals were purified by silica gel column chromatography (dichloromethane/methanol-90/10 (vol.)) to give {4- [ dimethoxy- (4-phenylthiophenyl) methyl group]Phenyl } diphenylsulfonium-nonafluorobutane sulfonate 3.2 g. The molar absorptivity at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol.

[ CHEMICAL 59 ]

< Synthesis of sulfonium salt 8 >

Synthesis example 23 Synthesis of 2- (4-bromophenyl) -2- (4-phenylthiophenyl) - [1,3] dioxolane

The same procedures as in Synthesis example 21 were repeated except for using ethylene glycol instead of methanol to give 5.0g of 2- (4-bromophenyl) -2- (4-phenylthiophenyl) - [1,3] dioxolane.

[ CHEM 60 ]

(Synthesis example 24) Synthesis of Diphenyl- {4- [2- (4-phenylthiophenyl) - [1,3] dioxolan-2-yl ] phenyl } sulfonium-nonafluorobutanesulfonate (sulfonium salt 8)

Using 2- (4-bromophenyl) -2- (4-thiophenylphenyl) - [1,3]Diphenyl- {4- [2- (4-phenylthiophenyl) - [1,3] diphenyl- {4- [2- (4-phenylthiophenyl) - [1,3] was prepared in the same manner as in Synthesis example 22, except that dioxolane was used in place of 4-bromo-4' -phenylthiophenyl benzophenone dimethylacetal]Dioxolan-2-yl]Phenyl } sulfonium-nonafluorobutane sulfonate 4.3 g. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol.

[ CHEM 61 ]

< Synthesis of sulfonium salt 9 >

(Synthesis example 25) Synthesis of dibenzothiophene-5-oxide

15g of dibenzothiophene was dissolved in 75g of formic acid, and 8.7g of a 35 mass% hydrogen peroxide solution was added dropwise thereto under ice cooling. Thereafter, the mixture was warmed to room temperature and stirred for 5 hours. After stirring, 200g of pure water was dropped into the reaction solution to precipitate a solid. The precipitated solid was filtered, washed 3 times with 40g of pure water and dried to obtain coarse crystals. The crude crystals were recrystallized from 100g of acetone and 200g of ethanol to obtain 12g of dibenzothiophene-5-oxide.

[ CHEM 62 ]

Synthesis example 26 Synthesis of 5- {4- [ dimethoxy- (4-phenylthiophenyl) methyl ] phenyl } dibenzothiophenium-nonafluorobutane sulfonate (sulfonium salt 9)

Synthesis example 22 was repeated in the same manner with the exception that dibenzothiophene 5-oxide was used in place of diphenylsulfoxide to give 5- {4- [ dimethoxy- (4-phenylthiophenyl) methyl]Phenyl } dibenzothiophenium-nonafluorobutane sulfonate 4.0 g. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol.

[ CHEM 63 ]

< Synthesis of sulfonium salt 10 >

Synthesis example 27 Synthesis of {4- [ dimethoxy- (4-phenylthiophenyl) methyl ] phenyl } (di-p-tolyl) sulfonium-p-toluenesulfonate (sulfonium salt 10)

Synthesis example 22 was repeated in the same manner with the exception that p-tolylsulfoxide was used instead of diphenylsulfoxide and sodium p-toluenesulfonate was used instead of potassium nonafluorobutane sulfonate to give {4- [ dimethoxy- (4-phenylthiophenyl) methyl group]Phenyl } (di-p-tolyl) sulfonium-p-toluenesulfonate 3.8 g. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol.

[ CHEM 64 ]

< Synthesis of sulfonium salt 11 >

Synthesis example 28 Synthesis of (6-methoxynaphthalen-2-yl) - (4-methylthiophenyl) methanone

The same procedures as in Synthesis example 1 above were repeated except for using 2-bromo-6-methoxynaphthalene instead of 4-bromobenzylsulfide and 4- (methylthio) benzoyl chloride instead of 4-fluorobenzoyl chloride to give 4.5g of (6-methoxynaphthalen-2-yl) - (4-methylthiophenyl) methanone.

[ CHEM 65 ]

Synthesis example 29 Synthesis of [4- (6-methoxynaphthalen-2-ylcarbonyl) phenyl ] dimethylsulfonium nonafluorobutanesulfonate (sulfonium salt 11)

The same procedures as in Synthesis example 3 above were repeated except for using (6-methoxynaphthalen-2-yl) - (4-methylthiophenyl) methanone instead of 4-methylthio-4' -phenylthiobenzophenone to give 4.5g of [4- (6-methoxynaphthalen-2-ylcarbonyl) phenyldimethylsulfonium-nonafluorobutanesulfonate. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁶ cm ² More than mol.

[ CHEM 66 ]

Synthesis example 30 Synthesis of {4- [ dimethoxy- (6-methoxynaphthalen-2-yl) methyl ] phenyl } dimethylsulfonium-nonafluorobutanesulfonate (sulfonium salt 11)

Use {4- (6-methoxynaphthalen-2-ylcarbonyl) phenyl } dimethylsulfonium-nonafluorobutane sulfonate instead of dimethyl- [4- (4-thiophenyl-benzoyl) phenyl]Synthesis example 4 was repeated in the same manner with the exception of sulfonium nonafluorobutane sulfonate to give {4- [ dimethoxy- (6-methoxynaphthalen-2-yl) methyl group]Phenyl } dimethylsulfonium-nonafluorobutane sulfonate 1.0 g. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² (iv) less than mol, and a molar absorption coefficient of 365nm of less than 1/10 min as compared with {4- (6-methoxynaphthalene-2-ylcarbonyl) phenyl } dimethylsulfonium-nonafluorobutane sulfonate obtained in Synthesis example 29.

[ CHEM 67 ]

< Synthesis of sulfonium salt 12 >

(Synthesis example 31) Synthesis of 6-bromonaphthoyl-2-chloride

The same procedures as in Synthesis example 12 above were repeated except for using 6-bromo-2-naphthoic acid instead of 2-thiophenylbenzoic acid to give 10.8g of 6-bromonaphthoyl-2-chloride.

[ CHEM 68 ]

Synthesis example 32 Synthesis of (6-bromonaphthalen-2-yl) - (4, 7-dimethoxynaphthalen-1-yl) methanone

The same procedures as in Synthesis example 20 above were repeated except for using 1, 6-dimethoxynaphthalene instead of diphenylsulfide and using 6-bromonaphthoyl-2-chloride instead of 4-bromobenzoyl chloride to obtain 5.4g of (6-bromonaphthalen-2-yl) - (4, 7-dimethoxynaphthalen-1-yl) methanone.

[ CHEM 69 ]

Synthesis example 33 Synthesis of 4- [ (6-bromonaphthalen-2-yl) dimethoxymethyl ] -1, 6-dimethoxynaphthalene

The same procedures used in Synthesis example 21 above were repeated except for using (6-bromonaphthalen-2-yl) - (4, 7-dimethoxynaphthalen-1-yl) methanone instead of 4-bromo-4' -phenylthiobenzophenone to give 5.1g of 4- [ (6-bromonaphthalen-2-yl) dimethoxymethyl ] -1, 6-dimethoxynaphthalene.

[ CHEM 70 ]

(Synthesis example 34) Synthesis of {6- [ (4, 7-Dimethoxynaphthalen-1-yl) dimethoxymethyl ] naphthalen-2-yl } diphenylsulfonium-nonafluorobutanesulfonate (sulfonium salt 12)

Using 4- [ (6-bromonaphthalen-2-yl) -dimethoxy-methyl]Synthesis example 22 was repeated in the same manner with the exception of using (E) -1, 6-dimethoxynaphthalene instead of 4-bromo-4' -phenylthiobenzophenone dimethyl acetal to obtain {6- [ (4, 7-dimethoxynaphthalen-1-yl) dimethoxymethyl group]Naphthalene-2-yl } diphenylsulfonium-nonafluorobutane sulfonate 4.0 g. The molar absorptivity at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol.

[ CHEM 71 ]

< Synthesis of sulfonium salt 13 >

Synthesis example 35 Synthesis of 4- (4-bromophenylthio) benzophenone

The same procedures as in Synthesis example 2 above were repeated except for using 4-fluorobenzophenone instead of 4-fluoro-4' -methylthiobenzophenone and using 4-bromophenylthiophenol instead of thiophenol to obtain 5.8g of 4- (4-bromophenylthio) benzophenone.

[ CHEM 72 ]

Synthesis example 36 Synthesis of 4- (4-bromophenylthio) benzophenone dimethyl acetal

The same procedures as in Synthesis example 21 were repeated except for using 4- (4-bromophenylthio) benzophenone instead of 4-bromo-4' -phenylthiobenzophenone, to give 5.1g of 4- (4-bromophenylthio) benzophenone dimethyl acetal.

[ CHEM 73 ]

Synthesis example 37 Synthesis of {4- [4- (dimethoxy-phenyl-methyl) phenylthio ] phenyl } diphenylsulfonium-nonafluorobutanesulfonate (sulfonium salt 13)

The same procedures as in Synthesis example 22 were repeated except for using 4- (4-bromophenylthio) benzophenone dimethyl acetal instead of 4-bromo-4' -thiophenylbenzophenone dimethyl acetal to obtain {4- [4- (dimethoxy-phenyl-methyl) thiophenyl ] phenyl acetal]Phenyl } diphenylsulfonium-nonafluorobutane sulfonate 4.0 g. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol.

[ CHEM 74 ]

< Synthesis of sulfonium salt 14 >

Synthesis example 38 Synthesis of (4-fluorophenyl) - (6-methoxynaphthalen-2-yl) methanone

The same procedures as in Synthesis example 1 above were repeated except for using 2-bromo-6-methoxynaphthalene instead of 4-bromothioanisole to give 4.3g of (4-fluorophenyl) - (6-methoxynaphthalen-2-yl) methanone.

[ CHEM 75 ]

Synthesis example 39 Synthesis of [4- (4-bromophenoxy) phenyl ] - (6-methoxynaphthalen-2-yl) methanone

The same procedures as in Synthesis example 2 above were repeated except for using (4-fluorophenyl) - (6-methoxynaphthalen-2-yl) methanone instead of 4-fluoro-4' -methylthiobenzophenone and using 4-bromophenol instead of thiophenol to give 5.9g of [4- (4-bromophenoxy) phenyl ] - (6-methoxynaphthalen-2-yl) methanone.

[ CHEM 76 ]

Synthesis example 40 Synthesis of 2- { [4- (4-bromophenoxy) phenyl ] -dimethoxymethyl } -6-methoxynaphthalene

The same procedures used in Synthesis example 20 above were repeated except for using [4- (4-bromophenoxy) phenyl ] - (6-methoxynaphthalen-2-yl) methanone instead of 4-bromo-4' -phenylthiobenzophenone to give 5.0g of 2- { [4- (4-bromophenoxy) phenyl ] -dimethoxymethyl } -6-methoxynaphthalene.

[ CHEM 77 ]

Synthesis example 41 Synthesis of {4- {4- [ dimethoxy- (6-methoxynaphthalen-2-yl) methyl ] phenoxy } phenyl } diphenylsulfonium-nonafluorobutanesulfonate (sulfonium salt 14)

2- { [4- (4-bromophenoxy) phenyl ] was used]Synthesis example 22 was repeated in the same manner with the exception of using (E) -dimethoxymethyl } -6-methoxynaphthalene in place of 4-bromo-4' -phenylthiobenzophenone dimethyl acetal to obtain {4- {4- [ dimethoxy- (6-methoxynaphthalen-2-yl) methyl ] n-butyl acetate]Phenoxy } phenyl } diphenylsulfonium-nonafluorobutane sulfonate 4.0 g. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol.

[ CHEM 78 ]

< Synthesis of iodonium salt 1>

(Synthesis example 42) Synthesis of 2, 4-dimethoxy-4' -iodobenzophenone

The same procedures as in Synthesis example 16 above were repeated except for using 4-iodobenzoyl chloride instead of 4-fluorobenzoyl chloride to give 5.3g of 2, 4-dimethoxy-4' -iodobenzophenone.

[ CHEM 79 ]

Synthesis example 43 Synthesis of (4-tert-butylphenyl) [4- (2, 4-dimethoxybenzoyl) phenyl ] iodonium-nonafluorobutane sulfonate

To 16g of sulfuric acid was added 4g of 2, 4-dimethoxy-4' -iodobenzophenone obtained in Synthesis example 41, and then 10g of potassium persulfate was added in small amounts in succession at 10 ℃ or lower, followed by stirring for 30 minutes. After stirring, 18g of tert-butylbenzene was added, and further stirring was carried out at 25 ℃ for 3 hours. After stirring, 30g of pure water was added at 10 ℃ or lower, and then 40g of methylene chloride and 3.7g of potassium nonafluorobutane sulfonate were added, followed by stirring at 25 ℃ for about 2 hours. The resulting mixture was washed with water 3 times, and dichloromethane was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography (dichloromethane/methanol 90/10 (vol.)) to give (4-tert-butylphenyl) [4- (2, 4-dimethoxybenzoyl) phenyl group]Iodonium nonafluorobutane sulfonate 3.5 g. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁶ cm ² More than mol.

[ CHEM 80 ]

Synthesis example 44 Synthesis of (4-tert-butylphenyl) {4- [ (2, 4-dimethoxyphenyl) dimethoxymethyl ] phenyl } iodonium-nonafluorobutane sulfonate (iodonium salt 1)

Using (4-tert-butylphenyl) [4- (2, 4-dimethoxybenzoyl) phenyl]Iodonium nonafluorobutane sulfonate instead of dimethyl- [4- (4-phenylthio-benzoyl) phenyl](4-tert-butylphenyl) [4- [ (2, 4-dimethoxyphenyl) dimethoxymethyl ] butane was obtained in the same manner as in Synthesis example 4 except for the sulfonium-nonafluorobutane sulfonate]Phenyl radical]Iodonium nonafluorobutane sulfonate 1.0 g. The molar absorptivity at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol, with (4-tert-butylphenyl) [4- (2, 4-dimethoxybenzoyl) phenyl ] obtained in Synthesis example 43]The molar absorption coefficient at 365nm of the iodonium nonafluorobutane sulfonate is 10 min or less than 1.

[ CHEMICAL 81 ]

< Synthesis of iodonium salt 2>

Synthesis example 45 Synthesis of (4, 7-dimethoxynaphthalen-1-yl) - (4-iodophenyl) methanone

The same procedures used in Synthesis example 19 above were repeated except for using 1, 6-dimethoxynaphthalene instead of diphenylsulfide and 4-iodobenzoyl chloride instead of 4-bromobenzoyl chloride to give 5.4g of (4, 7-dimethoxynaphthalen-1-yl) - (4-iodophenyl) methanone.

[ CHEM 82 ]

Synthesis example 46 Synthesis of [4- (4, 7-Dimethoxynaphthalen-1-ylcarbonyl) phenyl ] phenyliodonium-nonafluorobutane sulfonate

Synthesis example 42 was repeated in the same manner with the exception of using (4, 7-dimethoxynaphthalen-1-yl) - (4-iodophenyl) methanone instead of 2, 4-dimethoxy-4' -iodobenzophenone to obtain [4- (4, 7-dimethoxynaphthalen-1-ylcarbonyl) phenyl ] methyl acetate]3.3g of phenyliodonium nonafluorobutane sulfonate. The molar absorptivity at 365nm of the obtained compound was 1.0X 10 ⁶ cm ² More than mol.

[ CHEM 83 ]

Synthesis example 47 Synthesis of {4- [ (4, 7-dimethoxynaphthalen-1-yl) dimethoxymethyl ] phenyl } phenyliodonium-nonafluorobutane sulfonate (iodonium salt 2)

{4- (4, 7-Dimethoxynaphthalene-1-carbonyl) phenyl } phenyliodonium nonafluorobutane sulfonate was used instead of dimethyl- [4- (4-phenylthiobenzoyl) phenyl]Synthesis example 4 was repeated in the same manner with the exception of sulfonium nonafluorobutane sulfonate to give {4- [ (4, 7-dimethoxynaphthalen-1-yl) -dimethoxy-methyl]Phenyl } phenyliodonium-nonafluorobutane sulfonate 1.0 g. The molar absorptivity at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol, corresponding to {4- (4, 7-dimethoxynaphthalen-1-ylcarbonyl) obtained in Synthesis example 46) Phenyl } phenyliodonium-nonafluorobutane sulfonate has a molar absorption coefficient of 10 min to 1 at 365 nm.

[ CHEM 84 ]

< Synthesis of sulfonium salt 15 >

Synthesis example 48 Synthesis of {4- [ dimethoxy- (4-phenylthiophenyl) methyl ] phenyl } diphenylsulfonium-p-styrenesulfonate (sulfonium salt 15)

Synthesis example 22 was repeated in the same manner with the exception that sodium p-styrenesulfonate hydrate was used instead of potassium nonafluorobutane sulfonate to give {4- [ dimethoxy- (4-phenylthiophenyl) methyl ] sulfonate]Phenyl } diphenylsulfonium-p-styrene sulfonate 2.8 g. The molar absorption coefficient at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol.

[ CHEM 85 ]

< Synthesis of sulfonium salt 16 >

Synthesis example 49 Synthesis of {4- [ dimethoxy- (4-phenylthiophenyl) methyl ] phenyl } diphenylsulfonium- (4-methacryloyl-1, 1, 2-trifluorobutanesulfonate) (sulfonium salt 16)

Synthesis example 22 was repeated in the same manner with the exception of using sodium 4-methacryloyloxy-1, 1, 2-trifluorobutane sulfonate instead of potassium nonafluorobutane sulfonate to obtain {4- [ dimethoxy- (4-phenylthiophenyl) methyl ] butane sulfonate]Phenyl } diphenyl sulfonium- (4-methacryloyl-1, 1, 2-trifluorobutane sulfonate) 3.0 g. The molar absorptivity at 365nm of the obtained compound was 1.0X 10 ⁵ cm ² Less than mol.

[ CHEM 86 ]

< Synthesis of sulfonium salt 17 >

Synthesis example 50 Synthesis of 4-bromo-4' -phenylsulfinylbenzophenone

To 10.1g of 4-bromo-4' -phenylthiobenzophenone obtained in Synthesis example 20 was added 53.3g of formic acid, followed by stirring at 50 ℃ and successively dropwise addition of 2.9g of a 35% hydrogen peroxide solution at small amounts, followed by stirring at 50 ℃. After 1 hour, the reaction solution was cooled under ice-cooling, and 28.2g of pure water and 80.3g of toluene were added. After the organic layer was washed 3 times with 30g of pure water, the organic solvent was distilled off to obtain 10.0g of 4-bromo-4' -phenylsulfinylbenzophenone.

[ CHEM 87 ]

Synthesis example 51 Synthesis of 4- (4-hydroxyphenylthio) -4' -phenylsulfinylbenzophenone

7.7g of 4-bromo-4' -phenylsulfinylbenzophenone, 3.6g of potassium carbonate, and 3.0g of 4-hydroxythiophenol were dissolved in 23.1g of DMFb, and the mixture was stirred at 60 ℃. After 2 hours, the reaction solution was cooled under ice-cooling, and 70g of pure water was added dropwise to precipitate a solid. The precipitated solid was filtered and redissolved with 40g of dichloromethane. After washing 3 times with 40g of pure water, methylene chloride was distilled off to obtain crude crystals. The crude crystal was purified by silica gel column chromatography (hexane/ethyl acetate 2/1 (vol.)) to give 6.4g of 4- (4-hydroxyphenylthio) -4' -phenylsulfinylbenzophenone.

[ CHEM 88 ]

Synthesis example 52 Synthesis of 4- (4-hydroxyphenylthio) -4' -phenylsulfinylbenzophenone dimethyl Acetal

The same procedures as in Synthesis example 21 were repeated except for using 4- (4-hydroxyphenylthio) -4 ' -phenylsulfinylbenzophenone instead of 4-bromo-4 ' -phenylsulfinylbenzophenone, to give 5.0g of 4- (4-hydroxyphenylthio) -4 ' -phenylsulfinylbenzophenone dimethylacetal.

[ CHEM 89 ]

Synthesis example 53 Synthesis of (4- { dimethoxy- [4- (4-hydroxyphenylthio) phenyl ] methyl } phenyl) diphenylsulfonium-nonafluorobutane sulfonate (sulfonium salt 17)

5.0g of 4- (4-hydroxyphenylthio) -4' -phenylsulfinylbenzophenone dimethyl acetal was dissolved in 30.0g of dehydrated dichloromethane, and 6.8mL of a 2M phenylmagnesium chloride THF solution was added dropwise thereto under ice cooling. Thereafter, 1.7g of trichloromethylsilane was added dropwise thereto, followed by stirring for 1 hour. After stirring, 30g of a 10 mass% ammonium chloride aqueous solution was added at 5 ℃ or lower, followed by further stirring and washing with 5.0g of isopropyl ether 2 times. Thereafter, 40g of methylene chloride and 3.4g of potassium nonafluorobutane sulfonate were added, and the mixture was stirred at 25 ℃ for 2 hours. After the separation, the mixture was washed 3 times with 20g of pure water, and then dichloromethane was distilled off to obtain crude crystals. The crude crystal was purified by silica gel column chromatography (dichloromethane/methanol-90/10 (vol.)) to give 3.4g of (4- { dimethoxy- [4- (4-hydroxyphenylthio) phenyl ] methyl } phenyl) diphenylsulfonium-nonafluorobutane sulfonate.

[ CHEM 90 ]

< Synthesis of sulfonium salt 18 >

Synthesis example 54 Synthesis of (2-hydroxy-9-oxo-9H-fluoren-3-yl) diphenylsulfonium nonafluorobutanesulfonate

1.0g of 2-hydroxy-9-fluorenone, 1.0g of diphenyl sulfoxide, and 0.4g of phosphorus pentoxide were added to 6.0g of methanesulfonic acid, and the mixture was stirred under ice-cooling. After 18 hours, 20g of pure water was added dropwise to the reaction solution, and the mixture was washed 2 times with 5.0g of isopropyl ether. Thereafter, 20g of methylene chloride and 1.7g of potassium nonafluorobutane sulfonate were added, and the mixture was stirred at 25 ℃ for 2 hours. After the liquid separation, the mixture was washed 3 times with 10g of pure water, and methylene chloride was distilled off to obtain a crude crystal. The crude crystal was purified by silica gel column chromatography (dichloromethane/methanol 90/10 (vol.)) to give 2.1g of (2-hydroxy-9-oxo-9H-fluoren-3-yl) diphenylsulfonium-nonafluorobutanesulfonate.

[ CHEM 91 ]

Synthesis example 55 Synthesis of (2-hydroxy-9, 9-dimethoxy-9H-fluoren-3-yl) diphenylsulfonium-nonafluorobutane sulfonate

The same procedures as in Synthesis example 21 were repeated except for using 2.0g of (2-hydroxy-9-oxo-9H-fluoren-3-yl) diphenylsulfonium-nonafluorobutanesulfonate in place of 4-bromo-4' -phenylthiobenzophenone to obtain 2.1g of (2-hydroxy-9, 9-dimethoxy-9H-fluoren-3-yl) diphenylsulfonium-nonafluorobutanesulfonate.

[ CHEM 92 ]

Synthesis example 56 Synthesis of [ spiro (1, 3-dioxolan-2, 9 ' - [9H ] fluorene), 2 ' -hydroxy-3 ' -yl ] diphenylsulfonium-nonafluorobutanesulfonate (sulfonium salt 18)

2.0g of (2-hydroxy-9, 9-dimethoxy-9H-fluoren-3-yl) diphenylsulfonium nonafluorobutane sulfonate and 0.7g of ethylene glycol were dissolved in 16.0g of dehydrated THF16. Thereafter, 48.0mg of p-toluenesulfonic acid was added thereto, and the mixture was stirred at room temperature under a nitrogen atmosphere. After 18h, 0.2g triethylamine was added to the reaction solution. After THF was distilled off, 20g of methylene chloride and 20g of pure water were added. After the liquid separation, the mixture was washed 2 times with 20g of pure water, and methylene chloride was distilled off to obtain 1.8g of { spiro (1, 3-dioxolan-2, 9 ' - [9H ] fluorene), 2 ' -hydroxy-3 ' -yl } diphenylsulfonium-nonafluorobutane sulfonate.

[ CHEM 93 ]

< Synthesis of sulfonium salt 19 >

Synthesis example 57 Synthesis of 1- (6-methoxy-2-naphthyl) -3- (4-methylphenyl) -2-propen-1-one

1.6g of 2-acetyl-6-methoxynaphthalene and 1.1g of 4-methylbenzaldehyde were added to 16g of ethanol and stirred. 0.4g of a 10 mass% aqueous sodium hydroxide solution was added dropwise thereto under ice-cooling, and further stirred. After 3 hours, the solid precipitated in the reaction solution was filtered and washed with 8g of ethanol. The recovered solid was dried to obtain 2.2g of 1- (6-methoxy-2-naphthyl) -3- (4-methylphenyl) -2-propen-1-one.

[ CHEM 94 ]

Synthesis example 58 Synthesis of {6- [3- (4-methylphenyl) -1-oxo-2-propenyl ] -2-methoxynaphthalen-1-yl } diphenylsulfonium-nonafluorobutanesulfonate

0.8g of 1- (6-methoxy-2-naphthyl) -3- (4-methylphenyl) -2-propen-1-one and 0.3g of phosphorus pentoxide were added to 2.4g of methanesulfonic acid and stirred. To the mixture was added 0.4g of diphenyl sulfoxide successively in small amounts under ice-cooling, and the mixture was further stirred. After 3 hours, 20g of pure water was added dropwise under ice-cooling, followed by further stirring and washing with 5.0g of isopropyl ether 2 times. Thereafter, 20g of methylene chloride and 0.7g of potassium nonafluorobutane sulfonate were added thereto, and the mixture was stirred for 2 hours. After the liquid separation, the mixture was washed 3 times with 10g of pure water, and then dichloromethane was distilled off to obtain coarse crystals. The crude crystal was purified by silica gel column chromatography (dichloromethane/methanol-90/10 (vol.)) to give 0.9g of {6- [3- (4-methylphenyl) -1-oxo-2-propenyl ] -2-methoxynaphthalen-1-yl } diphenylsulfonium-nonafluorobutane sulfonate.

[ CHEM 95 ]

Synthesis example 59 Synthesis of {6- [3- (4-methylphenyl) -1, 1-dimethoxy-2-propenyl ] -2-methoxynaphthalen-1-yl } diphenylsulfonium-nonafluorobutanesulfonate (sulfonium salt 19)

The same procedures as in Synthesis example 4 above were repeated except for using {6- [3- (4-methylphenyl) -1-oxo-2-propenyl ] -2-methoxynaphthalen-1-yl } diphenylsulfonium-nonafluorobutanesulfonate instead of dimethyl- [4- (4-phenylthio) benzoylphenyl ] sulfonium-nonafluorobutanesulfonate to obtain {6- [3- (4-methylphenyl) -1, 1-dimethoxy-2-propenyl ] -2-methoxynaphthalen-1-yl } diphenylsulfonium-nonafluorobutanesulfonate 0.9 g.

[ CHEM 96 ]

< Synthesis of sulfonium salt 20 >

Synthesis example 60 Synthesis of 2, 3-dibromo-1- (6-methoxy-2-naphthyl) -3- (4-methylphenyl) -1-propanone

1.2g of 1- (6-methoxy-2-naphthyl) -3- (4-methylphenyl) -2-propen-1-one obtained in Synthesis example 57 was dissolved in 9.6g of dichloromethane. A solution of 2.0g of methylene chloride in which 1.0g of bromine was dissolved was added dropwise thereto under ice-cooling and stirred. After 2 hours, 5g of pure water was added to the reaction solution, followed by further stirring. After the liquid separation, the organic layer was washed 2 times with 5g of pure water, and the organic solvent was distilled off to obtain 1.8g of 2, 3-dibromo-1- (6-methoxy-2-naphthyl) -3- (4-methylphenyl) -1-propanone.

[ CHEM 97 ]

Synthesis example 61 Synthesis of 1- (6-methoxy-2-naphthyl) -3- (4-methylphenyl) -2-propyn-1-one

1.8g of 2, 3-dibromo-1- (6-methoxy-2-naphthyl) -3- (4-methylphenyl) -1-propanone and 0.8g of diazabicycloundecene were added to 14g of acetonitrile, and the mixture was stirred at room temperature. After 2h, 1.6g of potassium tert-butoxide was added and the mixture was further stirred. After 2 hours, 36g of pure water was added to the reaction solution to precipitate a solid. The precipitated solid was filtered, washed with 20g of pure water and dried to obtain 1.0g of 1- (6-methoxy-2-naphthyl) -3- (4-methylphenyl) -2-propyn-1-one.

[ CHEM 98 ]

Synthesis example 62 Synthesis of {6- [3- (4-methylphenyl) -1-oxo-2-propynyl ] -2-methoxynaphthalen-1-yl } diphenylsulfonium-nonafluorobutanesulfonate

The same procedures as in Synthesis example 58 were repeated except for using 1- (6-methoxy-2-naphthyl) -3- (4-methylphenyl) -2-propyn-1-one instead of 1- (6-methoxy-2-naphthyl) -3- (4-methylphenyl) -2-propen-1-one to give {6- [3- (4-methylphenyl) -1-oxo-2-propynyl ] -2-methoxynaphthalen-1-yl } diphenylsulfonium-nonafluorobutanesulfonate 0.8 g.

[ CHEM 99 ]

Synthesis example 63 Synthesis of {6- [3- (4-methylphenyl) -1, 1-dimethoxy-2-propynyl ] -2-methoxynaphthalen-1-yl } diphenylsulfonium-nonafluorobutanesulfonate (sulfonium salt 20)

The same procedures as in Synthesis example 4 were repeated except for using {6- [3- (4-methylphenyl) -1-oxo-2-propynyl ] -2-methoxynaphthalen-1-yl } diphenylsulfonium-nonafluorobutanesulfonate instead of dimethyl- [4- (4-thiophenyl) benzoylphenyl ] sulfonium-nonafluorobutanesulfonate to obtain 0.8g of {6- [3- (4-methylphenyl) -1, 1-dimethoxy-2-propynyl ] -2-methoxynaphthalen-1-yl } diphenylsulfonium-nonafluorobutanesulfonate.

[ CHEM 100 ]

< Synthesis of sulfonium salt 21 >

Synthesis example 64 Synthesis of 4-phenylthiobenzil

The same procedures as in Synthesis example 2 above were repeated except for using 1g of 4-chlorophenyl benzil instead of 4-fluoro-4' -methylthiobenzophenone to obtain 0.8g of 4-phenylthiophenyl benzil.

[ CHEM 101 ]

Synthesis example 65 Synthesis of [4- (benzoylcarbonyl) phenyl ] dimethylsulfonium nonafluorobutane sulfonate

0.8g of 4-phenylthiobenzil, 1.6g of diphenyliodonium-nonafluorobutane sulfonate and 55mg of copper acetate monohydrate were added to 8.0g of chlorobenzene, and the mixture was stirred at 80 ℃. After 2 hours, the reaction solution was cooled to 25 ℃ and 5.0g of pure water was added. After the liquid separation, the organic layer was washed 2 times with 5.0g of pure water, and the organic solvent was distilled off to obtain coarse crystals. The crude crystal was purified by silica gel column chromatography (dichloromethane/methanol 90/10 (vol.)) to give 1.0g of [4- (benzoylcarbonyl) phenyl ] dimethylsulfonium-nonafluorobutane sulfonate.

[ CHEMICAL 102 ] A method for producing a compound

Synthesis example 66 Synthesis of [4- (benzoyldimethoxymethyl) phenyl ] dimethylsulfonium-nonafluorobutanesulfonate (sulfonium salt 21)

The same procedures as in Synthesis example 4 above were repeated except for using [4- (benzoylcarbonyl) phenyl ] dimethylsulfonium-nonafluorobutane sulfonate instead of dimethyl- [4- (4-phenylthio) benzoylphenyl ] sulfonium-nonafluorobutane sulfonate to obtain 0.9g of [4- (benzoyldimethoxymethyl) phenyl ] dimethylsulfonium-nonafluorobutane sulfonate.

[ CHEM 103 ]

< Synthesis of sulfonium salt 22 >

Synthesis example 67 Synthesis of 4-bromo-4' - (4-methoxyphenyl) benzophenone

The same procedures as in synthesis example 16 were repeated except for using 4-bromobenzoyl chloride instead of 4-fluorobenzoyl chloride and 4-phenylanisole instead of 2, 4-dimethoxybenzene and changing the purification method from recrystallization from ethanol to silica gel column chromatography (hexane/ethyl acetate: 80/20 (vol.%)), thereby obtaining 3.1g of 4-bromo-4' - (4-methoxyphenyl) benzophenone.

[ CHEM 104 ]

Synthesis example 68 Synthesis of 4-bromo-4' - (4-methoxyphenyl) benzophenone dimethyl acetal

The same procedures as in Synthesis example 21 were repeated except for using 4-bromo-4 ' - (4-methoxyphenyl) benzophenone instead of 4-bromo-4 ' -phenylthiobenzophenone, to give 3.0g of 4-bromo-4 ' - (4-methoxyphenyl) benzophenone.

[ CHEM 105 ]

Synthesis example 69 Synthesis of [4- (4' -methoxybiphenyl-4-carbonyl) phenyl ] -diphenylsulfonium-nonafluorobutane sulfonate

The same operation as in synthesis example 22 was carried out except for using 4-bromo-4 ' - (4-methoxyphenyl) benzophenone dimethyl acetal instead of 4-bromo-4 ' -phenylthiobenzophenone dimethyl acetal and using a 10 mass% aqueous hydrochloric acid solution instead of a 10 mass% aqueous ammonium chloride solution, to obtain 4.7g of [4- (4 ' -methoxybiphenyl-4-carbonyl) phenyl ] -diphenylsulfonium-nonafluorobutanesulfonate.

[ CHEM 106 ]

Synthesis example 70 Synthesis of [4- (4' -hydroxybiphenyl-4-carbonyl) phenyl ] -diphenylsulfonium-nonafluorobutane sulfonate

4.0g of [4- (4' -methoxybiphenyl-4-carbonyl) phenyl ] -diphenylsulfonium-nonafluorobutane sulfonate was added to 40ml of acetic acid. 10.2g of 48 mass% aqueous HBr solution was added dropwise thereto at 70 ℃. After the dropwise addition, the mixture was stirred at 110 ℃ for 20 hours. Thereafter, 150g of water was added, and 40g of methylene chloride was added thereto with stirring. After the liquid separation, the mixture was washed with water 3 times, and then dichloromethane was distilled off to obtain a crude crystal. The crude crystal was purified by silica gel column chromatography (dichloromethane/methanol 90/10 (vol.)) to give 2.4g of [4- (4' -hydroxybiphenyl-4-carbonyl) phenyl ] -diphenylsulfonium-nonafluorobutane sulfonate.

[ CHEM 107 ]

Synthesis example 71 Synthesis of {4- [ (4' -hydroxybiphenyl-4-yl) dimethoxymethyl ] -phenyl } -diphenylsulfonium-nonafluorobutanesulfonate (sulfonium salt 22)

1.0g of [4- (4' -hydroxybiphenyl-4-carbonyl) phenyl ] -diphenylsulfonium-nonafluorobutane sulfonate obtained in Synthesis example 70 was dissolved in 2.5g of methanol, and 1.0g of trimethyl orthoformate and 4.0mg of concentrated sulfuric acid were added thereto, followed by stirring at 60 ℃ for 2 hours. After stirring, 0.5g of triethylamine was added, and the reaction solution was added to a mixed solution of 30g of dichloromethane and 10g of pure water and stirred for 10 minutes, thereby recovering an organic layer. The resulting organic layer was washed with water 3 times and then methylene chloride was distilled off to obtain {4- [ (4' -hydroxybiphenyl-4-yl) dimethoxymethyl ] -phenyl } -diphenylsulfonium-nonafluorobutanesulfonate 1.0 g.

[ CHEMICAL 108 ]

< Synthesis of sulfonium salt 23 >

Synthesis example 72 Synthesis of (6-bromo-naphthalen-2-yl) - (4-methoxyphenyl) methanone

The same procedures as in Synthesis example 16 above were repeated except for using 6-bromonaphthoyl chloride instead of 4-fluorobenzoyl chloride and anisole instead of 2, 4-dimethoxybenzene to give 4.1g of (6-bromo-naphthalen-2-yl) - (4-methoxyphenyl) methanone.

[ CHEM 109 ]

Synthesis example 73 Synthesis of (6-bromo-naphthalen-2-yl) - (4-methoxyphenyl) methanone dimethyl Acetal

The same procedures as in Synthesis example 21 were repeated except for using (6-bromo-naphthalen-2-yl) - (4-methoxyphenyl) methanone instead of 4-bromo-4' -benzenethiophenylbenzophenone to give 3.0g of (6-bromo-naphthalen-2-yl) - (4-methoxyphenyl) methanone dimethyl acetal.

[ CHEM 110 ]

Synthesis example 74 Synthesis of [6- (4-methoxybenzoyl) naphthalen-2-yl ] diphenylsulfonium-nonafluorobutane sulfonate

The same procedures as in Synthesis example 69 were repeated except for using (6-bromo-naphthalen-2-yl) - (4-methoxyphenyl) methanone dimethyl acetal instead of 4-bromo-4' - (4-methoxyphenyl) benzophenone dimethyl acetal to give 4.5g of [ [6- (4-methoxybenzoyl) naphthalen-2-yl ] diphenylsulfonium-nonafluorobutane sulfonate.

[ CHEM 111 ]

Synthesis example 75 Synthesis of [6- (4-hydroxybenzoyl) naphthalen-2-yl ] diphenylsulfonium-nonafluorobutane sulfonate

The same procedures as in synthetic example 70 above were repeated except for using [6- (4-methoxybenzoyl) naphthalen-2-yl ] diphenylsulfonium-nonafluorobutane sulfonate instead of [4- (4' -methoxybiphenyl-4-carbonyl) phenyl-diphenylsulfonium-nonafluorobutane sulfonate to obtain 3.8g of [6- (4-hydroxybenzoyl) naphthalen-2-yl ] diphenylsulfonium-nonafluorobutane sulfonate.

[ CHEM 112 ]

Synthesis example 76 Synthesis of {6- [ dimethoxy- (4-methoxyphenyl) methyl ] naphthalen-2-yl } diphenylsulfonium-nonafluorobutanesulfonate (sulfonium salt 23)

The same procedures used in Synthesis example 71 were repeated except for using [ [6- (4-hydroxybenzoyl) naphthalen-2-yl ] diphenylsulfonium-nonafluorobutane sulfonate instead of {4- [ (4' -hydroxybiphenyl-4-yl) dimethoxymethyl ] -phenyl } -diphenylsulfonium-nonafluorobutane sulfonate to obtain {6- [ dimethoxy- (4-methoxyphenyl) methyl ] naphthalen-2-yl } diphenylsulfonium-nonafluorobutane sulfonate (3.6 g).

[ CHEMICAL 113 ]

< Synthesis of Polymer A >

Synthesis example 50 Synthesis of Polymer A

8.0g of polyhydroxystyrene (weight-average molecular weight 8000) and 0.010g of 35 mass% aqueous hydrochloric acid were dissolved in 28g of dehydrated dioxane. 2.73g of cyclohexyl vinyl ether was dissolved in 2.80g of dehydrated dioxane, and added dropwise to the polyhydroxystyrene solution over 30 minutes. After the dropwise addition, the temperature was adjusted to 40 ℃ and the mixture was stirred for 2 hours. After stirring, the mixture was cooled, and then 0.014g of dimethylaminopyridine was added. Thereafter, the solution was dropwise added to 260g of pure water to precipitate a polymer. The resulting solid was washed 2 times with 300g of pure water and then vacuum-dried to obtain 9.2g of a white solid, a polymer shown below. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEMICAL 114 ]

< Synthesis of Polymer C >

Synthesis example 51 Synthesis of Polymer B

7.0g of acetoxystyrene, 3.1g of tert-butyl methacrylate, 0.022g of butylmercaptan and 0.40g of dimethyl-2, 2' -azobis (2-methylpropionate) (AIBN) were dissolved in 35g of Tetrahydrofuran (THF) and deoxygenated. This was added dropwise over 4 hours to 20g of THF, which had been fluidized with nitrogen and had been set to reflux temperature. After the dropwise addition, the mixture was stirred for 2 hours and then cooled to room temperature. This was added dropwise to a mixed solvent of 149g of hexane and 12g of THF to precipitate a polymer. The residue was separated by filtration under reduced pressure, and the obtained solid was washed with 52g of hexane and then dried under vacuum to obtain 10.3g of a polymer represented by the following formula B10 as a white solid. The weight average molecular weight of the polycarbonate resin composition was 9200 as determined in terms of polystyrene by gel permeation chromatography. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEM 115 ] to

Synthesis example 52 Synthesis of Polymer C

6.0g of Polymer B, 6.0g of triethylamine, 6.0g of methanol and 1.5g of pure water were dissolved in 30g of propylene glycol monomethyl ether, and the mixture was stirred at reflux temperature for 6 hours. Thereafter, the mixture was cooled to 25 ℃ and the resulting solution was added dropwise to a mixture of 30g of acetone and 30g of pure water to precipitate a polymer. The resulting solid was washed 2 times with 30g of pure water and then dried under vacuum to obtain 4.3g of a polymer C represented by the following formula as a white solid. The weight average molecular weight of the polycarbonate resin composition was 9100 as determined by gel permeation chromatography in terms of polystyrene. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEM 116 ]

< Synthesis of Polymer D >

Synthesis example 53 Synthesis of Polymer D

5.0g of α -methacryloyloxy- γ -butyrolactone, 6.0g of 2-methyladamantane-2-methacrylate, 4.3g of 3-hydroxyadamantane-1-methacrylate and 0.51g of dimethyl-2, 2' -azobis (2-methylpropionate) were dissolved in 26g of propylene glycol-1-monomethyl ether acetate (PGMEA) to be deoxygenated. It was added dropwise over 4 hours to 7.5g of PGMEA which had been previously heated to 85 ℃. Stirred for 2 hours and then cooled. After cooling, the mixture was added dropwise to 180g of hexane and reprecipitation was carried out. After filtration, the reaction mixture was dispersion-washed with 70g of hexane, filtered again, and then vacuum-dried to obtain 8.5g of a polymer D represented by the following formula, which was a compound reacted by the action of an acid. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEM 117 ]

< Synthesis of Polymer F >

Synthesis example 54 Synthesis of Polymer E

The same operation as in Synthesis example 51 was carried out except that p-t-butoxystyrene was used instead of t-butyl methacrylate, whereby 10.1g of a polymer represented by the following formula was obtained. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEM 118 ]

Synthesis example 55 Synthesis of Polymer F

The same operation as in Synthesis example 52 was carried out except that the polymer E was used in place of the polymer B, to obtain 4.1g of a polymer F represented by the following formula. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEM 119 ]

< Synthesis of Polymer G >

Synthesis example 56 Synthesis of Polymer G

The same procedures as in Synthesis example 53 above were repeated except for using 5.5G of 5-methacryloyloxynorbornane 2, 6-lactone, 6.2G of 4- (1-ethoxyethoxy) phenyl methacrylate and 4.4G of 4-hydroxyphenyl methacrylate as monomers to obtain 8.0G of a polymer G represented by the following formula. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEM 120 ]

< Synthesis of Polymer I >

Synthesis example 57 Synthesis of Polymer H

The same operation as in Synthesis example 51 was carried out except that 1-acetoxy-4-vinylnaphthalene was used instead of acetoxystyrene and 1- (2-tetrahydropyranyloxy) -4-vinylnaphthalene was used instead of tert-butyl methacrylate, to obtain H10.5g of a polymer represented by the following formula. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEM 121 ]

Synthesis example 58 Synthesis of Polymer I

The same operation as in synthesis example 52 was carried out except that polymer H was used instead of polymer B, to give polymer f4.3g represented by the following formula. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEM 122 ]

< Synthesis of Polymer J >

Synthesis example 59 Synthesis of Polymer J

The same procedures as in Synthesis example 53 above were repeated except that 2-methacryloxy-1, 3-propanesultone was used instead of α -methacryloxy- γ -butyrolactone, to give 8.0g of a polymer J represented by the following formula. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEM 123 ]

< Synthesis of Polymer K > (Synthesis example 60) Synthesis of Polymer K

The same procedures as in Synthesis example 53 above were repeated except for using 2-methacryloyloxy-1, 3-propanesultone instead of α -methacryloyloxy- γ -butyrolactone and using 1-ethoxyethyl methacrylate instead of 2-methyladamantane-2-methacrylate, to obtain 8.2g of a polymer K represented by the following formula. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEM 124 ]

< Synthesis of Polymer L >

Synthesis example 61 Synthesis of Polymer L

The same procedures as in Synthesis example 53 above were repeated except for using 7.2g of 5-methacryloyloxynorbornane 2, 6-sultone, 5.9g of 2- (1-ethoxyethoxy) -6-vinylnaphthalene and 3.0g of 2-hydroxy-6-vinylnaphthalene as monomers to obtain 8.0g of a polymer L represented by the following formula. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEM 125 ]

< Synthesis of Polymer M >

Synthesis example 62 Synthesis of Polymer M

The same procedures as in Synthesis example 53 were repeated except for using 164.7 g of the sulfonium salt obtained in Synthesis example 49, 3.9g of 5-methacryloyloxynorbornane 2, 6-lactone, 4.2g of 4- (1-ethoxyethoxy) phenyl methacrylate and 3.2g of 4-hydroxyphenyl methacrylate as monomers to obtain 7.8g of a polymer M represented by the following formula. The monomer ratio of the unit of the polymer in the present invention is not limited to the following ratio.

[ CHEM 126 ]

[ examples 1 to 32 ] and comparative examples 1 to 6 ]

< evaluation of Electron Beam sensitivity 1>

Samples were prepared as follows. To 3000mg of cyclohexanone, samples were prepared in the following proportions: 500mg of any one resin selected from the above polymers A, C and D; suitably one or more selected from the group consisting of 0.036mmol of each of the photoacid generator (PAG) and the sensitizing compound; and 0.0012mmol of an acid diffusion controller.

As the photo-acid generator (PAG), the above sulfonium salts 1 to 23, the below-mentioned sulfonium salts 24 and iodonium salts 1 to 2 are used. As the sensitizing compound, the sensitizing compound 1 shown below and comparative sensitizing compounds 1 'to 2' were used.

The sensitizing compound 1 was synthesized as follows. 5.0g of 4-methylthio-4' -phenylthiobenzophenone obtained in Synthesis example 2, 47mg of sulfuric acid and 13.5g of trimethyl orthoformate were dissolved in 12.5g of methanol, and the mixture was stirred at reflux temperature for 3 hours. Thereafter, the mixture was cooled to room temperature, 50g of a 5 mass% aqueous solution of sodium hydrogencarbonate was added thereto, and the mixture was further stirred for 10 minutes, and the precipitated crystals were filtered. The crystals were recovered and redissolved in 50g of ethyl acetate, followed by washing with water. Thereafter, ethyl acetate was distilled off to obtain 3.1g of 4-methylthio-4' -phenylthiobenzophenone dimethyl acetal.

[ CHEM 127 ]

The electron beam sensitivity evaluation was performed as follows. Sample 1 of the resist composition described above was spin-coated on a silicon wafer previously modified with hexamethylenedisilazane. This was prebaked on a hot plate at 110 ℃ for 1 minute to obtain a substrate having a coating film formed thereon and having a thickness of 200 nm. The coating film on the substrate was formed into a line and space pattern of 200nm by an electron beam of 30keV using an electron beam forming apparatus. The substrate irradiated with the electron beam was exposed to UV light at a dose of 500mJ/cm ² The entire surface was exposed to light of (1), and then the plate was heated at 110 ℃ for 1 minute. The resist was developed with a developer (product name: NMD-3; 2.38 mass% aqueous solution of tetramethylammonium hydroxide; manufactured by Tokyo Kasei Kogyo Co., Ltd.) for 1 minute, and then washed with pure water to obtain a 200nm line-and-space pattern. The electron beam irradiation amount at this time was set to E _size [μC/cm ² ]The sensitivity of electron beam irradiation was determined. In addition, the obtained good pattern was observed to determine LWR. To the other aboveThe samples were also subjected to sensitivity evaluation and LWR measurement as described above. The sample compositions and results are shown in tables 1 to 3.

In table 1, for the sensitivity and LWR of each sample, the sensitivity of the sample (comparative example 1) to which the sulfonium salt 24 and the comparative sensitizing compound 1' were added was set to 100, and the LWR was set to 1, and the evaluation results of the corresponding samples (examples 1 to 17 and comparative example 2) were calculated as relative values. The smaller the values of sensitivity and LWR, the more excellent the effect.

In table 2, the sensitivity of comparative example 3 is set to 100, the LWR is set to 1, and the evaluation results of the corresponding samples (examples 18 to 24 and comparative example 4) are calculated as relative values.

In table 3, the sensitivity of comparative example 5 is set to 100, the LWR is set to 1, and the evaluation results of the corresponding samples (examples 25 to 32 and comparative example 6) are calculated as relative values.

[ TABLE 1 ]

[ TABLE 2 ]

[ TABLE 3]

For any of the polymers, the samples containing the onium salts according to the several embodiments of the present invention, that is, examples 1 to 17, examples 18 to 24, comparative examples 3 and 4, and examples 25 to 32, comparative examples 5 and 6 all showed higher sensitivity than comparative examples 1 and 2.

The reason is considered as follows. In several embodiments of the present invention, the onium salt is deprotected by an acetal group under the action of an acid generated in the resist film by an electron beam as the 1 st active energy ray to form a ketone derivative. The ketone derivative absorbs UV as the 2 nd active energy ray, and thus can be excited by UV irradiation to directly generate an acid. On the other hand, in comparative examples 1 to 6, since a reaction accompanied by electron transfer, i.e., an intermolecular sensitizing reaction, such as a photo-electron transfer reaction, such as photosensitization, sensitivity was inferior and lower than that in the case where an acid was directly generated by excitation.

Further, by using the onium salt according to the embodiments of the present invention, since acid diffusion accompanied by electron transfer does not occur in acid generation by irradiation with the 2 nd active energy ray, LWR can be suppressed as compared with comparative examples 1 to 6 using an intermolecular sensitization reaction.

When example 13 and example 14 were compared with example 9 and example 12, respectively, it is considered that in example 13 and example 14, when the 2 nd active energy ray irradiation was performed, an acid was generated by excitation of the ketone derivative having absorption with respect to the 2 nd active energy ray, and when the 1 st active energy ray irradiation was performed, photosensitization occurred between the photosensitizing agent generated from the sensitizing compound 1 and the sulfonium salt 9 or the iodonium salt 1 having high electron-accepting property, and therefore, both of them were highly sensitive as compared with example 9 and example 12.

[ examples 1, 33 to 39 ] and comparative examples 1, 7 to 8 ]

< evaluation of Electron Beam sensitivity 2>

The same procedure as in example was repeated except that the PEB irradiation was carried out on a hot plate at 60 ℃ for 30 seconds after the electron beam irradiation<Electron Beam sensitivity evaluation 1>In the same operation, a line and space pattern of 200nm was obtained. The irradiation dose at this time was designated as E _size [μC/cm ² ]The sensitivity when PEB was performed after the electron beam irradiation was determined. In addition, the resulting pattern was observed to determine LWR. The sample compositions and results are shown in table 4. For the sensitivity and LWR of each sample (examples 33 to 39 and comparative example 8), the sensitivity of the sample (comparative example 7) to which the sulfonium salt 24 and the comparative sensitizing compound 1' were added was setThe LWR was set to 1, and the evaluation results of the samples corresponding thereto were calculated as relative values at 100.

In addition, in order to compare the effects of PEB, the sensitivity and LWR of the samples of example 1 and comparative example 1 relative to comparative example 7 were calculated and evaluated. In other words, in table 4, for comparison, the evaluation of example 1 (evaluation of the sample to which the sulfonium salt 1 and the sulfonium salt 24 were added, which was evaluated without PEB) and the evaluation of comparative example 1 (evaluation of the sample to which the sulfonium salt 24 and the comparative sensitizing compound 1' were added, which was evaluated without PEB) are described.

The smaller the values of sensitivity and LWR, the more excellent the effect.

[ TABLE 4 ]

In the pattern forming step, even when PEB was performed at 60 ℃ after electron beam irradiation, samples containing the onium salts according to several embodiments of the present invention, i.e., examples 33 to 39, were more sensitive than comparative examples 7 and 8 using an intermolecular sensitization reaction, and were able to suppress LWR, as in examples 1 to 32. In addition, when example 33, example 1 and comparative example 1 were compared, it is presumed that in example 33, the ketone derivative having an absorption with respect to the 2 nd active energy ray can be generated in a resist film more by diffusing the acid generated by the electron beam as the 1 st active energy ray by performing PEB after the electron beam irradiation, and thus the sensitivity is higher than in example 1 and comparative example 1 in which the PEB step is not performed after the electron beam irradiation.

In example 33, the LWR was slightly deteriorated as compared with example 1 due to the influence of acid diffusion by PEB, but since acid diffusion for variable-speed electron transfer did not occur in the generation of acid by the irradiation of the 2 nd energy ray, the LWR was suppressed as compared with comparative example 1 using sensitization reaction.

When example 35 and example 39 were compared, the polymer a had a higher proportion of hydroxystyrene and its derivatives having a lower ionization potential than the polymer C, and the secondary electron generation efficiency was slightly higher than that of the polymer C, and the acid generation efficiency of the electron beam as the 1 st active energy line was improved, and the activation energy of the acid-reactive group was low, and the deprotection reaction was efficiently performed, so that example 35 had a higher sensitivity than example 39.

[ examples 40 to 44 ] and comparative example 9 ]

< evaluation of Electron Beam sensitivity 3>

Carrying out the same as in the above-described embodiment<Electron Beam sensitivity evaluation 2>The same operation resulted in a line and space pattern of 200 nm. The irradiation dose at this time was designated as E _size [μC/cm ² ]The sensitivity of the PEB irradiated with the electron beam was determined. In addition, the obtained good pattern was observed to determine LWR. The sample compositions and results are shown in table 5. For the sensitivity and LWR of each sample (examples 40 to 44), the sensitivity of the sample (comparative example 9) to which the sulfonium salt 24 and the comparative sensitizing compound 1' were added was set to 100, and the LWR was set to 1, and the evaluation results of the corresponding sample were calculated as relative values.

The smaller the values of sensitivity and LWR, the more excellent the effect.

[ TABLE 5 ]

Examples 40 to 43, which are samples containing the onium salt according to the several embodiments of the present invention, have higher sensitivity and can suppress LWR as compared with comparative example 9 using the sensitization reaction between molecules, as in examples 1 to 32 described above. Further, it was found that, even when the onium salt of the present invention was contained in a polymer as in example 44, the same function as that of the sample to which the onium salt was added was exhibited, and it was possible to suppress LWR while achieving higher sensitivity than that of comparative example 9.

When examples 40 to 42 are compared, it is considered that by using the polymer containing the sultone compound as in examples 41 and 42, the acid generated by decomposition of the sultone compound after the irradiation with the electron beam as the 1 st active energy ray contributes to the deprotection reaction of the acetal of the onium salt according to the several embodiments of the present invention. This enables the production of a larger amount of ketone derivatives having absorption of the 2 nd active energy ray, and thus examples 41 and 42 have higher sensitivity than example 40. In example 42, since the acid-reactive compound is an acid-decomposable protecting group having a low activation energy, the acid generated by decomposition of the sultone compound after irradiation of the electron beam as the 1 st active energy ray also contributes to the polarity inversion by the reaction with the acid-reactive compound, and the solubility of the resin in the developer is further changed, so that the sensitivity is higher than that in example 41.

In comparison between examples 43 and 44, in example 44, since the anion part of the onium salt according to the present invention was copolymerized with the polymer, it is considered that the acids generated upon irradiation with the electron beam as the 1 st active energy ray and the 2 nd active energy ray were less likely to diffuse, and the LWR could be suppressed as compared with example 43.

Industrial applicability

According to some embodiments of the present invention, there is provided a resin composition containing an onium salt that is generated by a structural change of the onium salt by an active species generated by irradiation with a 1 st active energy ray such as an electron beam or an extreme ultraviolet ray, and generates an onium salt of the active species by irradiation with a 2 nd active energy ray. By using the resin composition, a resist composition having high sensitivity and excellent pattern characteristics such as LWR can be obtained.

Claims

1. A resist composition comprising a photoacid generator and an acid-reactive compound, wherein the photoacid generator comprises at least an onium salt represented by any one selected from the group consisting of the following general formula (1), the following general formula (11), the following general formula (12), and the following general formula (6),

the composition is used for a photolithography process using a 1 st active energy line and a 2 nd active energy line,

the 1 st active energy line is ArF excimer laser, electron beam or extreme ultraviolet,

the 2 nd active energy line is visible light or ultraviolet light,

the 1 st active energy line has a shorter wavelength than the 2 nd active energy line, or the photon or particle beam has a higher energy than the 2 nd active energy line,

[ CHEM 1 ]

[ CHEM 2 ]

In the formula (1), R ¹¹ And R ¹² Each independently is any one selected from the group consisting of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent(s) including a hydroxyl group, a cyano group, a mercapto group, a carboxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an aryl group, an aryloxy group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an N-alkyl-N-arylamino group, a phosphino group, a silyl group, a halogen atom, a trialkylsilyl group, a silyl group in which at least 1 alkyl group of a trialkylsilyl group is substituted with Ar, an alkylthio group and an arylthio group,

the R is ¹¹ 、R ¹² And at least two of the aryl groups bonded to the sulfonium group may form a ring structure directly with the sulfur atom bonded thereto by a single bond,

R ¹³ and R ¹⁴ Each independently is any one selected from the group consisting of an alkyl group, a hydroxyl group, an alkoxy group, an arylthio group, an aryl group, and an aryloxy group, and has 1 to 12 carbon atoms when having carbon atoms,

R ¹⁵ and R ¹⁶ Each independently is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms,

said R is ¹⁵ And R ¹⁶ Can be directly bonded to each other by a single bond to form a ring structure,

L ² is selected from a direct bond, an arylene group having 6 to 14 carbon atoms, orAnd an arylene group having 6 to 14 carbon atoms bonded to each other through an oxygen atom or a sulfur atom,

L ³ is a direct key and is characterized in that,

y is an oxygen atom, and Y is an oxygen atom,

h and i are each independently an integer of 1 to 3,

j is an integer of 0 to 4 when h is 1, j is an integer of 0 to 6 when h is 2, j is an integer of 0 to 8 when h is 3,

k is an integer of 0 to 5 when i is 1, k is an integer of 0 to 7 when i is 2, k is an integer of 0 to 9 when i is 3,

X ^- represents a monovalent counter anion of a monovalent group,

in the formula (11), R ¹¹ ～R ¹⁶ 、L ² Y, h-k and X ^- Each independently selected from R of said formula (1) ¹¹ ～R ¹⁶ 、L ² Y, h-k and X ^- The same selection items are respectively selected from the group,

L ⁴ and L ⁵ Each independently is any one selected from a direct bond, an alkenylene group having 2 carbon atoms, and an alkynylene group having 2 carbon atoms,

in the formula (12), R ¹⁷ Is aryl with 6-12 carbon atoms, L ² 、L ⁴ And L ⁵ Is a direct bond, R ¹³ 、R ¹⁴ 、R ¹⁵ 、R ¹⁶ Y, h-k and X ^- Each independently selected from R of said formula (1) ¹³ 、R ¹⁴ 、R ¹⁵ 、R ¹⁶ Y, h-k and X ^- The same selection items, respectively, are,

in the formula (6), R ¹¹ ～R ¹⁶ 、X ^- And Y are each independently selected from R of said formula (1) ¹¹ ～R ¹⁶ 、X ^- And Y are the same as each other,

R ¹⁸ is selected from any one of alkyl, hydroxyl, sulfydryl, alkoxy, alkyl carbonyl, aryl carbonyl, arylthio, alkylthio, aryl, heteroaryl, aryloxy, amino, cyano, nitro and halogen atoms, and has 1-12 carbon atoms when having carbon atoms,

e is an integer of 0 to 4,

f is an integer of 0 to 4,

g is an integer of 0 to 5.

2. The composition according to claim 1, wherein the onium salt is represented by any one selected from the general formula (11) and the general formula (12).

3. The composition of claim 1, further comprising an acid diffusion control agent.

4. The composition according to claim 1, wherein the acid-reactive compound is a resin B which changes its solubility in a developer by the action of an acid,

the resin B has at least one unit represented by the following general formulae (3a) to (3d),

[ CHEM 3]

In the formulae (3a) to (3d), R ¹ Is any one selected from a hydrogen atom, an alkyl group and a halogenated alkyl group,

R ² and R ³ Each independently a linear, branched or cyclic alkyl group,

R ⁴ is a linear, branched or cyclic alkyl group which may have a substituent C,

the substituent C is any one selected from the group consisting of a hydroxyl group, an alkoxy group, an oxo group, an amino group, and an alkylamino group,

the R is ² 、R ³ And R ⁴ 2 or more of them may be directly formed into a ring structure by a single bond,

R ⁵ and R ⁶ Each independently is any one selected from a hydrogen atom and a linear, branched or cyclic alkyl group,

R ⁷ is a linear, branched or cyclic alkyl group which may have a substituent D,

the substituent D is any one selected from the group consisting of a hydroxyl group, an alkoxy group, an oxo group, an amino group, and an alkylamino group,

the R is ⁵ 、R ⁶ And R ⁷ Wherein 2 or more of the above groups may form a ring structure directly with a single bond or form a ring structure via a methylene group,

L ¹ is any one selected from a direct bond, a carbonyloxy group, a carbonylamino group, a linear, branched or cyclic alkylenecarbonyloxy group, and an alkylenecarbonylamino group,

R ⁸ each independently is any one selected from the group consisting of an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, an amino group, a cyano group, a nitro group and a halogen atom,

l is an integer of 1 to 2,

m is an integer of 0 to 4 when l is 1, m is an integer of 0 to 6 when l is 2,

n is an integer of 1 to 5 when l is 1, n is an integer of 1 to 7 when l is 2,

m + n is 1 to 5 when l is 1, and m + n is 1 to 7 when l is 2.

5. The composition according to claim 4, wherein the resin B contains at least one of units represented by the following general formulae (4a) to (4B), or

The composition further comprises a resin C containing at least one of units represented by the following general formulae (4a) to (4b),

[ CHEM 4 ]

In the formulae (4a) and (4b), R ₁ 、R ₈ And L ₁ Each independently selected from the group consisting of R of the general formulae (3c) to (3d) ₁ 、R ⁸ And L ¹ The same selection items are respectively selected from the group,

R ⁹ is a compound containing a compound selected from the group consisting of-C (O) -O-, -SO ₂ and-O-SO ₂ -a cyclic group of at least any one of (a) to (b),

p is an integer of 0 to 4, and q is an integer of 1 to 5.

6. The composition of claim 1, wherein the photoacid generator is X in the onium salt ^- An acid generator unit-containing resin having a unit represented by the following general formula (5),

[ CHEM 5 ]

In the formula (5), R ¹ Is any one selected from a hydrogen atom, an alkyl group and a halogenated alkyl group,

Z ¹ is any one selected from the group consisting of a linear or branched alkylene group having 1 to 12 carbon atoms, a linear or branched alkenylene group having 1 to 12 carbon atoms, and an arylene group having 6 to 14 carbon atoms,

some or all of the hydrogens of the alkylene, alkenylene, and arylene groups may be replaced with fluorine atoms.

7. A method of manufacturing a device, comprising the steps of:

a step of applying the composition according to any one of claims 1 to 6 on a substrate to form a resist film;

irradiating the resist film with a 1 st active energy ray;

irradiating the resist film irradiated with the 1 st active energy ray with a 2 nd active energy ray; and

and a step of obtaining a pattern by developing the resist film after the irradiation with the 2 nd active energy ray.

8. The method for manufacturing a device according to claim 7, wherein the wavelength of the 1 st active energy ray is shorter than the wavelength of the 2 nd active energy ray.

9. The method of manufacturing a device according to claim 7, wherein the 1 st active energy ray is an electron beam or an extreme ultraviolet ray.

10. The method of manufacturing a device according to claim 7, wherein a step of heating with an electric heating wire or a laser is included between the step of irradiating the 1 st active energy ray and the step of irradiating the 2 nd active energy ray.

11. The method for manufacturing a device according to any one of claims 7 to 10, wherein the 1 st active species is generated from the composition in a resist film by irradiation of the 1 st active energy line,

the structure of the photoacid generator is changed by the 1 st active species,

and generating the 2 nd active species from the photo-acid generator with the modified structure by irradiating the 2 nd active energy line.

12. The method of manufacturing a device according to claim 11, wherein the structurally-modified photoacid generator is a ketone derivative.